Multi-layer curable compositions containing 1,1-di-activated vinyl compound products and related processes

ABSTRACT

Multi-layer coatings comprising polymerization reaction products of 1,1-di-activated vinyl compounds are described. Also provided are processes for coating substrates with curable compositions comprising 1,1-di-activated vinyl compounds. Also provided are articles coated with this composition.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. application Ser. No.16/320,534, which was filed on Jan. 25, 2019, which is a U.S. nationalstage application, filed under 35 U.S.C. § 371, of InternationalApplication No. PCT/US2017/044032, which was filed on Jul. 26, 2017, andwhich claims priority to U.S. Provisional Application No. 62/454,965,which was filed on Feb. 6, 2017, U.S. Provisional Application No.62/372,365, which was filed on Aug. 9, 2016, and U.S. ProvisionalApplication No. 62/366,781, which was filed on Jul. 26, 2016. Thecontents of each are incorporated by reference into this specification.

BACKGROUND OF THE INVENTION

Curable compositions can be applied to a wide variety of substrates toprovide color and/or other visual effects, corrosion resistance,adhesion, sealability, abrasion resistance, chemical resistance, and thelike. For example, multi-layer coatings often include a basecoat layerthat provides color and/or other visual effects and a topcoat layer,which sometimes comprises a clearcoat layer, and which provides anabrasion and scratch resistant layer. With respect to multi-layercoatings applied to metal substrates, such as automotive substrates, forexample, a primer layer and/or a surface passivation layer may beapplied to the bare metal substrate underneath overlying basecoats andtopcoats. Generally, each layer of a multi-layer coating is separatelydehydrated and/or cured under varying conditions, such as at differentflashing and/or baking temperatures, for example, to form the finalmulti-layer coating.

SUMMARY OF THE INVENTION

A multi-layer coating comprises a first coating layer applied over atleast a portion of a substrate, and a second coating layer applied overat least a portion of the first coating layer. The first coating layerand the second coating layer both independently comprise a polymericresin. The first coating layer and/or the second coating layer, whencured, comprise a polymerization reaction product of a 1,1-di-activatedvinyl compound, or a multifunctional form thereof, or a combinationthereof.

A process for coating a substrate comprises applying a first coatinglayer over at least a portion of a substrate, applying a second coatinglayer over at least a portion of the first coating layer, and curing thefirst coating layer and/or the second coating layer. The first coatinglayer and the second coating layer both independently comprise apolymeric resin. The first coating layer and/or the second coatinglayer, when cured, comprise a polymerization reaction product of a1,1-di-activated vinyl compound, or a multifunctional form thereof, or acombination thereof.

It is understood that the invention described in this specification isnot necessarily limited to the examples summarized in this Summary.

DETAILED DESCRIPTION OF THE INVENTION

A “curable composition” as used in this specification refers to acomposition that has one or more components that can participate in acuring transformation. The composition can undergo a change in itsphysical properties, over a period of time, as a result of chemicaland/or physical processes. A curable composition may be curable at roomtemperature or a lower temperature, or may require exposure to elevatedtemperature such as a temperature above room temperature or othercondition(s) to initiate and/or to accelerate the curing transformation.Once a curable composition is applied to a surface (and duringapplication), the curing reaction can proceed to provide a curedcomposition. A cured composition develops a tack-free surface, cures,and then fully cures over a period of time. A composition is consideredfully cured when the hardness no longer increases. Curable compositionsprovided by the present disclosure may be applied directly onto thesurface of a substrate as a single layer (often referred to as monocoat)or a multi-layer and/or over an underlayer such as a primer by anysuitable process.

The curable compositions provided by the present disclosure may be used,for example, in sealants, coatings, adhesives, encapsulants, and pottingcompositions. A sealant refers to a composition capable of producing afilm that has the ability to resist operational conditions, such asmoisture and temperature, and at least partially block the transmissionof materials, such as water, fuel, and other liquids and gases. Asealant can be used to seal surfaces, smooth surfaces, fill gaps, sealjoints, seal apertures, and other features. A coating refers to acurable composition that is deposited on an article that serves toprotect the article and/or improve the appearance of the coated article.Examples include pigmented coatings that provide color to automobiles,airplanes, ships or free-standing structures such as metallic cans,buildings or bridges. An encapsulant refers to a curable compositionthat is applied on at least a portion of a material to increasedurability and/or modulate the workable life of the material. Examplesof encapuslants include films of polymeric ethylvinyl actetate used tocover parts of photovoltaic modules, to protect the modules from harshenvironmental factors. A “putty” or “potting composition” refers tocurable composition that is applied to a surface as a filler to smoothensurface irregularities and/or improve appearance. Examples of theapplication of putty include, but are not limited to, the repair ofscratches, holes, deformities, and dents in automobile parts. Otherexamples of the application of putty include filling cracks in woodwork,securing glass and/or smoothening surfaces in buildings, particularly,walls and ceilings. Adhesives refer to curable compositions utilized tobond together two or more substrate materials. For example, structuraladhesives may be used for binding together automotive or industrialcomponents. As used in this disclosure the phrase “curable compositionlayer” is meant to include sealant, coating, adhesive, encapsulant, andpotting composition layers that may be applied over a substrate or overother curable composition layers. For convenience and/or illustrationpurposes, this disclosure may refer to single or multiple “coatingcomposition layers.” However, the use of the phrase “coating compositionlayer” is used herein for illustrative purposes only, and should beunderstood to include the various other sealant, adhesive, encapsulant,and potting composition layers that are contemplated as possiblealternatives. Accordingly, except as described in the present examples,the phrase “coating composition layer” can be used interchangeably tomean any other curable composition layer contemplated herein, such as asealant, coating, adhesive, encapsulant, and potting composition layer,as determined by one of ordinary skill in the art.

As used in this specification, particularly in connection with coatinglayers or films, the terms “on,” “onto,” “over,” and variants thereof(e.g., “applied over,” “formed over,” “deposited over,” “provided over,”“located over,” and the like), mean applied, formed, deposited,provided, or otherwise located over a surface of a substrate, but notnecessarily in contact with the surface of the substrate. For example, acoating layer “applied over” a substrate does not preclude the presenceof one or more other coating layers of the same or different compositionlocated between the applied coating layer and the substrate. Likewise, asecond coating layer “applied over” a first coating layer does notpreclude the presence of one or more other coating layers of the same ordifferent composition located between the applied second coating layerand the applied first coating layer.

As used in this specification, the terms “polymer” and “polymeric” meansprepolymers, oligomers, and both homopolymers and copolymers. As used inthis specification, “prepolymer” means a polymer precursor capable offurther reactions or polymerization by one or more reactive groups toform a higher molecular mass or crosslinked state.

In addition, when used in the specification, a “first coating layer” or“second coating layer” may include, separately, one or more coatingapplications to form either the first or second coating layer.Accordingly a “coating layer” as identified herein does not preclude thepresence of one or more other coating applications of the same ordifferent composition to form that layer. For example, where the firstcoating layer is a basecoat layer it is contemplated at one, two, ormore basecoat applications may be used together to form the “firstcoating layer.” Similarly, a clearcoat can be contemplated to have one,two or more clearcoat applications to form the “second coating layer”.

As used in this specification, the prefix “poly” refers to two or more.For example, a “polyfunctional” molecule (whether a polymer, monomer, orother compound) comprises two or more reactive functional groups such ashydroxyl groups, amine groups, mercapto groups, carbamate groups, andthe like. More specifically, “polyol” means a compound comprising two ormore hydroxyl groups, “polyamine” means a compound comprising two ormore amine groups, “polythiol” means a compound comprising two or moremercapto groups, and “polycarbamate” means a compound comprising two ormore carbamate groups.

A polyfunctional compound such as a polyol, polyamine, polythiol, orpolycarbamate may be a polymer, but does not have to be a polymer, andmay comprise, for example, non-polymeric compounds. A polymeric polyol,polymeric polyamine, polymeric polythiol, or polymeric polycarbamaterespectively comprises two or more pendant and/or terminal hydroxyl,amine, mercapto, or carbamate functional groups on the polymermolecules. A “pendant group” refers to a group that comprises anoffshoot from the side of a polymer backbone and which does not comprisepart of the polymer backbone, whereas “terminal group” refers to a groupon an end of a polymer backbone and which comprises part of the polymerbackbone.

Additionally, the terms polyol, polyamine, polythiol, and polycarbamatemay encompass compounds comprising combinations of different types offunctional groups. For example, a compound comprising two or morehydroxyl groups and two or more carbamate groups may be referred to as apolyol, a polycarbamate, or a polyol/polycarbamate. Furthermore, polyol,polyamine, polythiol, and polycarbamate compounds may comprise either orboth the neutral functional groups (hydroxyl, amine, mercapto, orcarbamate) and/or a salt of an ionized form of the functional group(e.g., alkoxide salts, ammonium salts, and the like).

As used in this specification, the term “1,1-di-activated vinylcompound” means a compound comprising a vinyl group having two electronwithdrawing groups (EWG) covalently bonded to one of the π-bondedcarbons and no substituents covalently bonded to the other π-bondedcarbon (i.e., -EWG-C(═CH₂)-EWG-), wherein the electron withdrawinggroups independently comprise halogen groups, haloalkyl groups,carbonyl-containing groups (e.g., esters, amides, aldehydes, ketones,acyl halides, carboxylic/carboxylate groups), cyano groups, sulfonategroups, ammonium groups, quaternary amine groups, or nitro groups. Theterm “multifunctional form” means a compound comprising two or more1,1-di-activated vinyl groups covalently bonded in one molecule. Forinstance, a dialkyl methylene malonate is an example of a1,1-di-activated vinyl compound, and a transesterification adduct of adialkyl methylene malonate and a polyol is an example of amultifunctional form of a dialkyl methylene malonate.

The multi-layer coatings described in this specification contain atleast two coating layers, both of which independently comprise apolymeric resin, and at least one of which comprises a polymerizationreaction product of a 1,1-di-activated vinyl compound, or amultifunctional form thereof, or a combination thereof. The two coatinglayers can thus comprise the same polymeric resin or different polymericresins, provided that at least one of the two coating layers comprisesthe polymerization reaction product. The polymerization reaction productcan alone comprise the polymeric resin of the coating layer or layerscontaining the polymerization reaction product, or the coating layer orlayers can further comprise one or more different, additional polymericresins and/or other polyfunctional compounds.

The 1,1-di-activated vinyl compounds can comprise methylene dicarbonylcompounds, dihalo vinyl compounds, dihaloalkyl disubstituted vinylcompounds, or cyanoacrylate compounds, or multifunctional forms of anythereof, or combinations of any thereof. Examples of 1,1-di-activatedvinyl compounds and multifunctional forms thereof that can be used toformulate curable compositions to form one or more coating layers in themulti-layer coatings are described in U.S. Pat. Nos. 8,609,885;8,884,051; 9,108,914; 9,181,365; and 9,221,739, which are incorporatedby reference into this specification. Additional examples of1,1-di-activated vinyl compounds and multifunctional forms thereof thatcan be used to formulate curable compositions to form one or morecoating layers in the multi-layer coatings are described in U.S.Publication Nos. 2014/0288230; 2014/0329980; and 2016/0068618, which areincorporated by reference into this specification.

The coating layers can comprise a polymerization reaction product of a1,1-di-activated vinyl compound comprising a methylene malonate or amultifunctional form thereof, or a combination thereof. Methylenemalonates are compounds having the general formula (I):

wherein R and R′ may be the same or different and may represent nearlyany substituent or side-chain, such as substituted or unsubstitutedalkyl or aryl groups. For example, the coating layers can comprise apolymerization reaction product of a dialkyl methylene malonate, adiaryl methylene malonate, a multifunctional form of a dialkyl methylenemalonate, or a multifunctional form of a diaryl methylene malonate, or acombination of any thereof.

A multifunctional form of a methylene malonate can comprise atransesterification adduct of the methylene malonate and a polyol. Amultifunctional form of a methylene malonate can thus have the generalformula (II):

wherein n is greater than one, X is a polyol residue, and each R may bethe same or different, as described above. As used herein the term“residue” refers to a group derived from the respective compound. Forinstance, in the above formula, X is an n-valent group derived from apolyol by a transesterification reaction involving methylene malonateand n hydroxyl groups of said polyol. Likewise, a polymer comprisingresidues of a certain compound is obtained from polymerizing saidcompound. In some examples, a multifunctional form of a methylenemalonate can comprise a transesterification adduct of the methylenemalonate and a diol, and thus have the general formula (III):

wherein X is a diol residue and R and R′ may be the same or different,as described above.

Polyols that are suitable for the production of a transesterificationadduct with a methylene malonate include, for example, polymeric polyols(such as polyether polyols, polyester polyols, acrylic polyols, andpolycarbonate polyols) and monomeric polyols (such as alkane polyols,including alkane diols such as 1,5-pentanediol and 1,6-hexanediol). Thetransesterification adduct can be formed by the reaction of a methylenemalonate and a polyol, in the presence of a catalyst, in a suitablereaction medium. Examples of transesterification adducts of methylenemalonates and polyols that may be used in the curable compositions aredescribed in U.S. Publication No. 2014/0329980 and U.S. Pat. No.9,416,091, which are incorporated by reference herein. Further, theconcentration of the transesterification adduct can be influenced byratio of the reactants and/or distillation or evaporation of thereaction medium.

In some examples, the coating layers of the multi-layer coatings cancomprise a polymerization reaction product of dimethyl methylenemalonate (D3M), a multifunctional form of D3M, or both. In someexamples, the coating layers of the multi-layer coatings can comprise apolymerization reaction product of diethyl methylene malonate (DEMM), amultifunctional form of DEMM, or both. The multifunctional forms of D3Mor DEMM can comprise transesterification adducts of D3M or DEMM and apolyol, such as, for example, 1,5-pentanediol or 1,6-hexanediol.

In some examples, the coating layers of the multi-layer coatings cancomprise a polymerization reaction product of a combination of a dialkylmethylene malonate and a multifunctional form of a dialkyl methylenemalonate. The coating layers of the multi-layer coatings can comprise,for example, a polymerization reaction product of DEMM and amultifunctional form of DEMM comprising a transesterification adduct ofDEMM and at least one polyol. The DEMM can be transesterified with apolyol comprising, for example, an alkane diol such as 1,5-pentanediolor 1,6-hexanediol.

In some examples, the curable compositions used to form the coatinglayers of the multi-layer coatings can comprise (in addition to the1,1-di-activated vinyl compound, or a multifunctional form thereof, or acombination thereof) a polyol, a polyamine, a polythiol, or apolycarbamate, or a combination of any thereof. While not intending tobe bound by any theory, it is believed that the vinyl group(s) in the1,1-di-activated vinyl compounds and/or the multifunctional formsthereof can react via a Michael addition mechanism with the hydroxyl,amine, mercapto, and/or carbamate groups in polyol, polyamine,polythiol, and/or polycarbamate resins or other compounds (i.e.,polyfunctional polymeric resins or polyfunctional monomeric compounds),and thereby form stable covalent linkages. Additionally, the1,1-di-activated vinyl compounds and/or the multifunctional formsthereof can undergo self-polymerization reactions, thereby forming thepolymerization reaction product, which may covalently bond topolyfunctional polymeric resins or polyfunctional monomeric compoundsthrough the linkages formed by the Michael addition reactions with thehydroxyl, amine, mercapto, and/or carbamate groups. Therefore, the1,1-di-activated vinyl compounds and/or the multifunctional formsthereof can function as crosslinking/curing agents for polyfunctionalpolymeric resins or polyfunctional monomeric compounds. In some example,the 1,1-di-activated vinyl compounds and/or the multifunctional formsthereof can provide a multiple-cure mechanism comprising both Michaeladdition reactions and polymerization reactions that crosslink and curepolyfunctional polymeric resins or polyfunctional monomeric compounds.

Polyfunctional polymeric resins that can be used to formulate curablecompositions to form one or more coating layers in the multi-layercoatings, and which are crosslinked and cured with the 1,1-di-activatedvinyl compounds and/or the multifunctional forms thereof, includepolymeric resins comprising pendant and/or terminal hydroxyl, amine,mercapto, and/or carbamate groups, such as, for example, polyetherpolyols, polyester polyols, acrylic polyols, polycarbonate polyols,polyether polyamines, polyester polyamines, acrylic polyamines,polycarbonate polyamines, polyether polythiols, polyester polythiols,acrylic polythiols, polycarbonate polythiols, polyether polycarbamates,polyester polycarbamates, acrylic polycarbamates, polycarbonatepolycarbamates, and combinations of any thereof. Additionalpolyfunctional polymeric resins that can be formulated in curablecompositions and crosslinked and cured with 1,1-di-activated vinylcompounds and/or the multifunctional forms thereof include anypolyfunctional polymeric resins that incorporate hydroxyl, amine,mercapto, or carbamate groups, or combinations of any thereof, includingfor example, polyester resins, polyurethane resins, polyurea resins,polyether resins, polythioether resins, polycarbonate resins,polycarbamate resins, epoxy resins, phenolic resins, and aminoplastresins (urea-formaldehyde and/or melamine-formaldehyde).

In addition to, or in lieu of, polyfunctional polymeric resins,polyfunctional monomeric compounds can be formulated in the curablecompositions and crosslinked and cured with 1,1-di-activated vinylcompounds and/or the multifunctional forms thereof. If polyol compoundsare used, they may be the same as or different from those used forforming the transesterification adducts described above. Examples ofmonomeric polyol compounds include, but are not necessarily limited to,glycols such as ethylene glycol, diethylene glycol, triethylene glycol,1,2-propylene glycol, 1,3-butylene glycol, tetramethylene glycol,hexamethylene glycol, neopentyl glycol, pentaerythritol, andcombinations of any thereof. Other suitable hydroxyl-containingpolyfunctional monomeric compounds include, but are not limited to,1,5-pentandiol, 1,6-hexanediol, cyclohexanedimethanol,2-ethyl-1,6-hexanediol, 1,4-butanediol, 1,3-propanediol, trimethylolpropane, 1,2,6-hexanetriol, glycerol, and combinations of any thereof.Additionally, monomeric amino alcohols that can be formulated in thecurable compositions and crosslinked and cured with 1,1-di-activatedvinyl compounds and/or the multifunctional forms thereof include, butare not limited to, ethanolamine, propanolamine, butanolamine, andcombinations of any thereof.

Examples of monomeric polyamine compounds that can be formulated incurable compositions used to form one or more coating layers in themulti-layer coatings, and crosslinked and cured with 1,1-di-activatedvinyl compounds and/or the multifunctional forms thereof, include, forexample, diamines such as, for example, ethylenediamine,hexamethylenediamine, 1,2-propanediamine,2-methyl-1,5-penta-methylenediamine, 2,2,4-trimethyl-1,6-hexanediamine,isophoronediamine, diaminocyclohexane, xylylenediamine,1,12-diamino-4,9-dioxadodecane, and combinations of any thereof. Othersuitable monomeric and polymeric polyamine compounds includepolyetheramines such as the Jeffamine® products available from HuntsmanChemical Company.

Examples of monomeric and polymeric polythiol compounds that can beformulated in curable compositions used to form one or more coatinglayers in the multi-layer coatings, and crosslinked and cured with1,1-di-activated vinyl compounds and/or the multifunctional formsthereof, include, for example, resins and compounds produced by theesterification of a polyol with a mercapto organic acid. Examples ofsuitable polyols include the polyols described above, and examples ofsuitable mercapto organic acids include thioglycolic acid andmercaptopropionic acid. Examples of monomeric polythiol compoundsinclude, but are not limited to, glyceryl dithioglycolate, glyceryltrithioglycolate, glycol dimercaptoacetate, pentaerythritoltetramercaptoacetate, glycol di-(3-mercaptopropionate), pentaerythritoltetra(3-mercaptoproprionate), dipentaerythritolhexa(3-mercaptopropionate), trimethylolpropane tris-(thioglycolate),pentaerythritol tetrakis-(thioglycolate), ethyleneglycoldithioglycolate, trimethylolpropane tris-(βthiopropionate),pentaerythritol tetrakis-W-thiopropionate), dipentaerythritolpoly(β-thiopropionate), and combinations of any thereof. Other suitablemonomeric and polymeric polythiol compounds include the Thiocure®products available from Bruno Bock Chemische Fabrik GmbH & Co. KG.

Examples of monomeric and polymeric polycarbamate compounds that can beformulated in curable compositions used to form one or more coatinglayers in the multi-layer coatings, and crosslinked and cured with1,1-di-activated vinyl compounds and/or the multifunctional formsthereof, include, for example, resins and compounds produced by thetranscarbamylation of a polyol with an alkyl carbamate (i.e., thetransesterification of the alkyl carbamate with the polyol).

In addition to the 1,1-di-activated vinyl compound, or multifunctionalform thereof, or combination thereof, the curable compositions used toform one or more coating layers in the multi-layer coatings can furthercomprise an activator. As used in this specification, the term“activator” means a compound or other agent capable of initiating and/orcatalyzing (i) polymerization of 1,1-di-activated vinyl compounds ormultifunctional forms thereof and/or (ii) addition reactions between1,1-di-activated vinyl compounds or multifunctional forms thereof andpolyfunctional components (e.g., polyol, polyamine, polythiol, and/orpolycarbamate resins or compounds). The term “activator” includes (1)active forms of activator compounds and (2) latent precursor forms ofactivator compounds that are capable of conversion from the latentprecursor form into the active form (e.g., by exposure to an effectiveamount of heat, electromagnetic radiation, pressure, or a chemicalco-activator). Additionally, latent precursor forms of activatorcompounds that are capable of conversion into the active form includeactivators associated with a volatile or otherwise removableneutralizing agent or inhibitor compound that can evaporate or otherwisebe removed from the curable composition when applied as a coating layer,thereby activating the activator.

The activator can comprise a base. As used in this specification, theterm “base” means an electronegative compound or functional groupcapable of initiating the anionic polymerization of a 1,1-di-activatedvinyl compound. Suitable activators include organic bases (e.g.,amine-containing compounds and carboxylate salts), inorganic bases(e.g., hydroxide salts, carbonate salts, and metal oxides),organometallic compounds, and combinations of any thereof. Suitableactivators also include polymers comprising pendant and/or terminalamine, carboxylate salt, or other base functionality capable ofinitiating the anionic polymerization of a 1,1-di-activated vinylcompound.

In some examples, the activator comprises a strong base (pH over 9, inwater at 25° C.), a moderate base (pH from 8-9, in water at 25° C.), ora weak base (pH from over 7 to 8, in water at 25° C.), or a combinationof any thereof. The activator may comprise, for example, sodium acetate;potassium acetate; acid salts of sodium, potassium, lithium, copper, orcobalt; tetrabutyl ammonium fluoride, chloride, or hydroxide; an amine,including primary, secondary, and tertiary amines; an amide; salts ofpolymer bound acids; benzoate salts; 2,4-pentanedionate salts; sorbatesalts; propionate salts; secondary aliphatic amines; piperidene,piperazine, N-methylpiperazine, dibutylamine, morpholine, diethylamine,pyridine, triethylamine, tripropylamine, triethylenediamine,N,N-dimethylpiperazine, butylamine, pentylamine, hexylamine,heptylamine, nonylamine, decylamine; 1,4-diazabicyclo[2.2.2]octane(DABCO); 1,1′-iminobis-2-propanol (DIPA); 1,2-cyclohexaneamine;1,3-cyclohexandimethanamine; 2-methylpentamethylenediamine;3,3-iminodipropylamine; triacetone diamine (TAD); salts of amines withorganic monocarboxylic acids; piperidine acetate; metal salt of a lowermonocarboxylic acid; copper(II) acetate, cupric acetate monohydrate,potassium acetate, zinc acetate, zinc chloracetate, magnesiumchloracetate, magnesium acetate; salts of acid containing polymers;salts of polyacrylic acid co-polymers; and combinations of any thereof.

In some examples, the curable compositions used to form one or morecoating layers in the multi-layer coatings can comprise a tertiary amineactivator such as, for example, DABCO; 2-(dimethylamino)ethanol(DMAE/DMEA); 2-piperazin-1-ylethylamine;N,N,N′,N′-tetrakis(2-hydroxypropyl)ethylenediamine;2-[2-(dimethylamino)ethoxy]ethanol;1-[bis[3-(dimethylamino)propyl]amino]-2-propanol;N,N,N′,N″,N″-pentamethyldiethylenetriamine;N,N,N′,N′-tetraethyl-1,3-propanediamine;N,N,N,N′-tetramethyl-1,4-butanediamine;N,N,N,N′-tetramethyl-1,6-hexanediamine;1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane;1,3,5-trimethylhexahydro-1,3,5-triazine; methyl dicocoamine;1,8-diazabicycloundec-7-ene (DBU); 1,5 diazabicyclo-[4,3,0]-non-5-ene(DBN); 1,1,3,3-tetramethylguanidine;1,5,7-Triazabicyclo[4.4.0]dec-5-ene;7-Methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene; or combinations of anythereof. In some examples, a tertiary amine activator comprises abicyclic guanidine compound or a substituted derivative thereof, suchas, for example, 1,5,7-Triazabicyclo[4.4.0]dec-5-ene; or7-Methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, or a substitutedderivative of either thereof, or a combination of any thereof.

The activator can comprise an ionic liquid. As used herein, the term“ionic liquid” means a salt having a melting point temperature of lessthan 100° C. at 1 atmosphere of pressure. Ionic liquids can be in aliquid state at room temperature (approximately 23° C.) and atmosphericpressure. Ionic liquids comprise a cation ionically associated with ananion. The cations can comprise, for example, heterocyclicnitrogen-containing organic cations such as imidazolium cations,pyrazolium cations, pyrrolidinium cations, pyridinium cations,pyrazinium cations, or pyrimidinium cations, including derivativesthereof; or other cations such as, for example, C¹-C³²tetraalkylphosphonium cations, C¹-C³² tetraalkylammonium cations, orC¹-C³² trialkylsulfonium cations. The anions can comprise, for example,a halide (F⁻, Cl⁻, Br⁻, I⁻), formate, acetate, nitrate, phosphate,sulfonate, tetrafluoroborate, hexfluorophosphate, triflate(trifluoromethane sulfonate), bis(trifluoromethylsulfonyl)imide,tosylate, an alkyl sulfonate anion (e.g., methyl sulfonate), analkylsulfate anion, a carboxylate anion, or a phthalate anion.

The ionic liquid activators used in the compositions, coatings, andprocesses described in this specification can comprise any combinationof the above-described cations and anions that initiate and/or catalyze(i) polymerization of 1,1-di-activated vinyl compounds ormultifunctional forms thereof and/or (ii) addition reactions between1,1-di-activated vinyl compounds or multifunctional forms thereof andpolyfunctional components (e.g., polyol, polyamine, polythiol, and/orpolycarbamate resins or compounds).

The ionic liquid activator can comprise an imidazolium salt of theformula:

wherein R¹ and R² are each independently a C₁-C₁₂ alkyl group; R³, R⁴,and R⁵ are each independently a hydrogen or a C₁-C₁₂ alkyl group, and X⁻is an anion. In some examples, R¹ and R² are each a C₁-C₁₂ alkyl group;and R³, R⁴, and R⁵ are each a hydrogen atom. In some examples, R¹, R²,and R³ are each a C₁-C₁₂ alkyl group; and R⁴ and R⁵ are each a hydrogenatom.

The ionic liquid activator can comprise a pyrazolium salt of theformula:

wherein R¹ and R² are each independently a C₁-C₁₂ alkyl group; R³, R⁴,and R⁵ are each independently a hydrogen or a C₁-C₁₂ alkyl group, and X⁻is an anion. In some examples, R¹ and R² are each a C₁-C₁₂ alkyl group;and R³, R⁴, and R⁵ are each a hydrogen atom. In some examples, R¹, R²,and R³ are each a C₁-C₁₂ alkyl group; and R⁴ and R⁵ are each a hydrogenatom.

The ionic liquid activator can comprise a pyridinium salt of theformula:

wherein R¹ is a C₁-C₁₂ alkyl group; R² are each independently a C₁-C₁₂alkyl group, n is 0 to 5, and X⁻ is an anion.

The ionic liquid activator can comprise a pyrimidinium salt and/or apyrazinium salt of the formulas:

wherein R¹ is a C₁-C₁₂ alkyl group; R² are each independently a C₁-C₁₂alkyl group, n is 0 to 4, and X⁻ is an anion.

The ionic liquid activator can comprise an ammonium salt and/or aphosphonium salt of the formulas:

wherein R¹, R², R³, and R⁴ are each independently a C₁-C₁₂ alkyl group;and X⁻ is an anion.

The anion (X⁻) in the salts described above can comprise, for example, ahalide (F⁻, Cl⁻, Br⁻, I⁻), formate, acetate, nitrate, phosphate,sulfonate, tetrafluoroborate, hexfluorophosphate, triflate(trifluoromethane sulfonate), bis(trifluoromethylsulfonyl)imide,tosylate, an alkyl sulfonate anion (e.g., methyl sulfonate), analkylsulfate anion, a carboxylate anion, or a phthalate anion.

The ionic liquid activators used in the compositions, coatings, andprocesses described in this specification can comprise any combinationof the above-described cations and anions, and can also comprisecombinations of any two or more ionic liquids each independentlycomprising the above-described cations and anions.

The curable compositions can comprise an activator in amounts, based ontotal composition weight, ranging from a non-zero amount up to 10%, upto 5%, up to 2%, up to 1%, up to 0.5%, or up to 0.1%, or any sub-rangesubsumed within such ranges. The activators may be maintained separatefrom the 1,1-di-activated vinyl compounds or multifunctional formsthereof (e.g., in separate container) until a time sufficiently close tothe application of the curable composition over a substrate in order toprevent premature curing of the curable composition. The activator maythen be mixed with all of the other components of the curablecomposition and applied over a substrate using a suitable applicationtechnique (e.g., spraying, electrostatic spraying, dipping, rolling,brushing, troweling electrocoating, and the like). In other examples,described below, activators may be applied over and/or under layers ofthe curable compositions to (1) activate addition reactions between thepolyfunctional components and the 1,1-di-activated vinyl compounds ormultifunctional forms thereof, and/or (2) activate polymerizationreactions among the 1,1-di-activated vinyl compounds or multifunctionalforms thereof.

In some examples, an activator may comprise a metal oxide layer on ametallic substrate over which the curable compositions are applied. Forexample, chromium oxide films on stainless steel substrates, aluminumoxide films on aluminum or aluminum oxide substrates, or titanium oxidefilms on titanium or titanium alloy substrates can function asactivators in coating layers applied over such substrates.

Additional examples of activators and activation methods that can beused in connection with one or more coating layers in the multi-layercoatings are described in U.S. Pat. No. 9,181,365, which is incorporatedby reference into this specification.

In some examples, particularly, but not necessarily, where the curablecompositions used to form one or more coating layers in the multi-layercoatings comprise both (1) the 1,1-di-activated vinyl compound, ormultifunctional form thereof, or combination thereof, and (2) a polyol,polyamine, polythiol, or polycarbamate, or combinations of any thereof,the curable compositions can further comprise an acid promoter. In someexamples, the acid promoter can comprise a strong acid. As used in thisspecification, the term “strong acid” means an acid having a pKa inwater of less than −1.74 and, for protic acids, at least one proton (H⁺)that completely dissociates in dilute aqueous solution. Strong acidpromoters that can be formulated in the curable compositions include,for example, inorganic strong acids and organic strong acids. Suitableinorganic strong acids include, for example, mineral acids (e.g.,hydrochloric acid, perchloric acid, sulfuric acid, and nitric acid) andheteropoly acids (e.g., phosphotungstic acid, phosphomolybdic acid,silicotungstic acid, and silicomolybdic acid). Suitable organic strongacids include, for example, sulfonic acids (e.g., p-toluenesulfonicacid, methanesulfonic acid, and dodecylbenzenesulfonic acid).Combinations of any strong acids (e.g., a mixture of a sulfonic acid anda heteropoly acid) may also be formulated in the curable compositions.

Without intending to be bound by any theory, it is believed that acidsmay function as Lewis acids in the curable compositions and complex tothe 1,3-dicarbonyl motif, thereby promoting a Michael addition reactionbetween the functional groups on polyfunctional components and the vinylgroups on the 1,1-di-activated vinyl compound and/or multifunctionalform thereof. Accordingly, a strong acid component in a curablecomposition may shift the crosslinking and curing reactions away fromself-polymerization of the 1,1-di-activated vinyl compound and/ormultifunctional form thereof and toward Michael addition reactionsforming covalent linkages between the polyfunctional components and the1,1-di-activated vinyl compound and/or multifunctional form thereof.

In some examples, particularly, but not necessarily, where the curablecompositions used to form one or more coating layers in the multi-layercoatings comprise an activator, the curable compositions can furthercomprise an extender. As used in this specification, the term “extender”means a compound or other agent capable of decreasing the reaction rateof (i) polymerization of 1,1-di-activated vinyl compounds ormultifunctional forms thereof and/or (ii) addition reactions between1,1-di-activated vinyl compounds or multifunctional forms thereof andpolyfunctional components (e.g., polyol, polyamine, polythiol, and/orpolycarbamate resins or compounds). Accordingly, extenders function toextend the pot life of the curable compositions and can be used incombination with activators and/or acid promoters, as described above,to control the pot life and cure response of the curable compositionsused to form one or more coating layers in the multi-layer coatings.

The extenders used in the compositions, coatings, and processesdescribed in this specification can comprise, for example, a carboxylicanhydride compound and/or a carboxylic acid compound. Suitablecarboxylic anhydride compounds include, for example, unsaturatedanhydrides such as maleic anhydride; citraconic anhydride; itaconicanhydride; aconitic anhydride;bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride; crotonicanhydride; 1-cyclopentene-1,2-dicarboxylic anhydride; methacrylicanhydride; or combinations of any thereof. Suitable carboxylic anhydridecompounds also include, for example, saturated anhydrides such as thesaturated homologues of any of the above-described unsaturatedanhydrides (e.g., succinic anhydride). Suitable carboxylic acidcompounds include, for example, short-chain (e.g., C₂ to C₂₀) saturatedand unsaturated carboxylic acids such as oxalic acid, acetic acid,propionic acid, octanoic, stearic acid, isostearic acid, benzoic acid,citric acid, (meth)acrylic acid, crotonic acid, isocrotonic acid,vinylacetic acid, 2-pentenoic acid, 3-pentenoic acid, allylacetic acid,maleic acid, fumaric acid, citraconic acid, itaconic acid, aconiticacid, saturated and unsaturated fatty acids (e.g., palmitoleic acid,vaccenic acid, and/or oleic acid), and combinations of any thereof.

Alternatively, or in addition, the extenders used in the compositions,coatings, and processes described in this specification can comprise,for example, an anhydride-containing vinyl polymer and/or a carboxylicacid-containing vinyl polymer. As used in this specification, the term“vinyl polymer” means any polymer produced by addition reactions betweencarbon-carbon double bonds. Anhydride-containing vinyl polymers can beproduced from monomer mixtures comprising an ethylenically unsaturatedcarboxylic acid anhydride such as, for example, maleic anhydride;citraconic anhydride; itaconic anhydride; aconitic anhydride;bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride; crotonicanhydride; 1-cyclopentene-1,2-dicarboxylic anhydride; methacrylicanhydride; or combinations of any thereof. Anhydride-containing vinylpolymers can be produced from monomer mixtures further comprisingethylenically unsaturated monomers such as, for example, styrene andderivatives thereof, vinyl acetate, vinyl chloride, (meth)acrylateesters, and the like. Anhydride-containing vinyl polymers suitable foruse as extenders in the compositions, coatings, and processes describedin this specification are described, for example, in U.S. Pat. No.4,798,745 at column 7, line 27 to column 8, line 3, and at column 10,line 40 to column 12, line 59, which is incorporated by reference intothis specification.

Carboxylic acid-containing vinyl polymer suitable for use as extendersin the compositions, coatings, and processes described in thisspecification can be produced from monomer mixtures comprising anethylenically unsaturated carboxylic acid such as, for example,(meth)acrylic acid, crotonic acid, isocrotonic acid, vinylacetic acid,2-pentenoic acid, 3-pentenoic acid, allylacetic acid, maleic acid,fumaric acid, citraconic acid, itaconic acid, aconitic acid, saturatedand unsaturated fatty acids (e.g., palmitoleic acid, vaccenic acid,and/or oleic acid), and combinations of any thereof. Carboxylicacid-containing vinyl polymers can be produced from monomer mixturesfurther comprising ethylenically unsaturated monomers such as, forexample, styrene and derivatives thereof, vinyl acetate, vinyl chloride,(meth)acrylate esters, and the like. Additionally, vinyl polymerscontaining both carboxylic acid groups and carboxylic acid anhydridegroups can be used as extenders in the compositions, coatings, andprocesses described in this specification. Such vinyl polymer can beproduced from monomer mixtures comprising both an ethylenicallyunsaturated carboxylic acid and an ethylenically unsaturated carboxylicacid anhydrides, as described above.

In some examples, the curable compositions used to form one or morecoating layers in the multi-layer coatings can comprise (1) the1,1-di-activated vinyl compound, or multifunctional form thereof, orcombination thereof, and (2) any combination of an acid promoter, anactivator, and/or an extender, as described above. The curablecompositions used to form one or more coating layers in the multi-layercoatings can further comprise (3) a polyol, polyamine, polythiol, orpolycarbamate, or combinations of any thereof. The curable compositionsused to form one or more coating layers in the multi-layer coatings canfurther comprise additional materials such as additional resins,solvents, reactive diluents, colorants, and the like. As used herein,“colorant” means any substance that imparts color and/or other opacityand/or other visual effect to a curable composition, particularly whenapplied over a substrate and cured. A colorant can be added to a curablecomposition in any suitable form, such as discrete particles,dispersions, solutions, and/or flakes. A single colorant or a mixture oftwo or more colorants can be formulated in a curable composition used toform one or more coating layers in the multi-layer coatings described inthis specification.

Example colorants include pigments (organic or inorganic), dyes, andtints, such as those used in the paint industry and/or listed by the DryColor Manufacturers Association (DCMA), as well as special effectcompositions. A colorant may include, for example, a finely dividedsolid powder that is insoluble, but wettable, under the conditions ofuse. A colorant can be organic or inorganic and can be agglomerated ornon-agglomerated. Colorants can be incorporated into a curablecomposition by use of a grind vehicle, such as an acrylic grind vehicle,the use of which will be familiar to persons skilled in the art.

Example pigments and/or pigment compositions include, but are notlimited to, carbazole dioxazine crude pigment, azo, monoazo, diazo,naphthol AS, salt type (flakes), benzimidazolone, isoindolinone,isoindoline and polycyclic phthalocyanine, quinacridone, perylene,perinone, diketopyrrolo pyrrole, thioindigo, anthraquinone, indanthrone,anthrapyrimidine, flavanthrone, pyranthrone, anthanthrone, dioxazine,triarylcarbonium, quinophthalone pigments, diketo pyrrolo pyrrole red(“DPPBO red”), titanium dioxide, carbon black, and mixtures of anythereof. The terms “pigment” and “colored filler” can be usedinterchangeably. Example dyes include, but are not limited to soluble inorganic solvents and/or water such as phthalo green or blue, iron oxide,bismuth vanadate, anthraquinone, perylene, and quinacridone.

Example tints include, but are not limited to, pigments dispersed inwater-based or water miscible carriers such as AQUA-CHEM 896 (availablefrom Degussa, Inc.), and CHARISMA COLORANTS and MAXITONER INDUSTRIALCOLORANTS (available from the Accurate Dispersions Division of EastmanChemical Company).

A colorant optionally formulated in a curable composition can alsocomprise a special effect composition or pigment. As used herein, a“special effect composition or pigment” means a composition or pigmentthat interacts with visible light to provide an appearance effect otherthan, or in addition to, a continuous unchanging color. Example specialeffect compositions and pigments include those that produce one or moreappearance effects such as reflectance, pearlescence, metallic sheen,texture, phosphorescence, fluorescence, photochromism, photosensitivity,thermochromism, goniochromism, and/or color-change. Examples of specialeffect compositions can include transparent coated mica and/or syntheticmica, coated silica, coated alumina, aluminum flakes, a transparentliquid crystal pigment, a liquid crystal coating, and combinations ofany thereof.

Other examples of materials that can be formulated in a curablecomposition include plasticizers, abrasion resistant particles,anti-oxidants, hindered amine light stabilizers, UV light absorbers andstabilizers, surfactants, flow and surface control agents, thixotropicagents, solvents and co-solvents, reactive diluents, catalysts, reactioninhibitors, and other customary auxiliaries in the paint and coatingindustry.

The invention described in this specification includes the use of acurable composition, as described above, to produce a multi-layercoating. For example, a process for coating a substrate can compriseapplying a first coating layer over at least a portion of a substrate,applying a second coating layer over at least a portion of the firstcoating layer, and curing the first coating layer and/or the secondcoating layer. The curing of the first coating layer and the secondcoating layer can be performed sequentially or simultaneously with orwithout intermediate flashing, drying, or dehydrating steps. The firstcoating layer and the second coating layer both independently comprise apolymeric resin. The first coating layer and/or the second coatinglayer, when cured, comprise a polymerization reaction product of a1,1-di-activated vinyl compound, or a multifunctional form thereof, or acombination thereof. The first coating layer and/or the second coatinglayer, when cured, may also comprise an addition reaction product of a1,1-di-activated vinyl compound, or a multifunctional form thereof, or acombination thereof and a polyol, polyamine, polythiol, orpolycarbamate.

The “Addition Reaction product” refers to the adduct formed by thereaction of 1,1′-di-activated vinyl compound and/or multifunctional formthereof with a nucleophile (such as an amine, thiol or alcohol and/ortheir polymeric form). Without being bound to any theory, this may bethe result of an addition of the nucleophile to the conjugate doublebond (‘the Michael Addition Reaction’), or displacing the alcohol of theester of a 1,1-diactivated vinyl ester with a another alcohol (atrans-esterification reaction), an amine, a thiol and/or a polymericform of them. For example, the reaction of an amine can result in anamide product and the reaction with a thiol can result in a thioesterproduct. A “polymeric addition product” refers to the product ofpolymerization reaction, wherein a multitude of reactants reactrepetitively. Without being bound by any theory, this could be donethrough a variety of reaction mechanisms, such as anionicpolymerization, condensation polymerization, chain growth or radicalpolymerization. For example, a primary amine can react 1,1′-diethylmethylene malonate (DEMM) via anionic polymerization to formpolymeric-DEMM.

The first coating layer and/or the second coating layer can comprise acurable composition having, in any combination, any of the features orcharacteristics described above. For example, the 1,1-di-activated vinylcompound can comprise a methylene dicarbonyl compound, a dihalo vinylcompound, a dihaloalkyl disubstituted vinyl compound, or a cyanoacrylatecompound, or a multifunctional form of any thereof, or a combination ofany thereof. The curable composition forming a coating layer can includean activator (e.g., an amine such as a tertiary amine like DABCO orDMAE/DMEA, or an ionic liquid). The curable composition forming acoating layer can include a promoter (e.g., a strong acid such as asulfonic acid and/or a heteropoly acid), particularly in examplesfurther comprising a polyol, polyamine, polythiol, or polycarbamate,which can comprise a polyfunctional polymeric resin or a polyfunctionalmonomeric compound or a combination thereof. The curable compositionforming a coating layer can include an extender (e.g., ananhydride-containing vinyl polymer).

As described above, the curable composition used to form one or morecoating layers in the multi-layer coatings can comprise any combinationof an acid promoter, an activator compound, and/or an extender. Withoutintending to be bound by any theory, the presence of an acid promoterand/or an activator compound and/or an extender in a curable compositioncan influence the final coating properties by modulating the curekinetics and/or the extent of Michael addition reactions versusself-polymerization of the 1,1-di-activated vinyl compound and/ormultifunctional form thereof. In some examples, the acid catalyst cancomprise a “strong acid” as described above and/or weaker acids.Suitable weaker acids that can be formulated in the curable compositionsinclude, for example, inorganic weak acids and organic weak acids. Inthis context, weak acids are defined as having pKa in the range of −1.3to 7 in water at 25° C. Suitable inorganic weak acids include, forexample, sulfamic acid, phosphoric acid, hypochlorous acid, and boricacid. Suitable organic weak acids include, for example, carboxylic acidssuch as oxalic acid, acetic acid, propionic acid, octanoic, stearicacid, isostearic acid, benzoic acid, and citric acid.

As used in this specification, the terms “cure” and “curing” refer tothe progression of a liquid curable composition from the liquid state toa cured state and encompass physical drying of curable compositionsthrough solvent or carrier evaporation (e.g., thermoplastic curablecompositions) and/or chemical crosslinking of components in the curablecompositions (e.g., thermosetting curable compositions). In this regard,the term “cured,” as used in this specification, refers to the conditionof a liquid curable composition in which a film or layer formed from theliquid curable composition is at least set-to-touch.

In some examples, the curing of the first coating layer and/or thesecond coating layer can comprise spraying an activator solution overand/or under at least a portion of the first coating layer and/or thesecond coating layer. The activator solution can comprise an activator(as described above) dissolved or otherwise dispersed in a liquidcarrier. The activator solution can comprise an activator compound suchas amine activator (e.g., a tertiary amine compound such as DABCO orDMAE/DMEA) dissolved in an aqueous or organic solvent (e.g., an estersolvent such as n-butyl acetate). The activator solution can be sprayedor otherwise applied over a substrate and a curable composition appliedover the pre-applied activator solution. Alternatively, or in addition,the activator solution can be sprayed or otherwise applied over apre-applied layer or film of a curable composition. The activatorsolution may initiate polymerization reactions and/or Michael additionreactions at the interface of the applied curable composition layer orfilm and may migrate into the layer or film to further initiate curingreactions.

In some examples, the curing of the first coating layer may be initiatedby activator compounds present in the second coating layer, or thecuring of the second coating layer may be initiated by activatorcompounds present in the first coating layer. For instance, the firstcoating layer may comprise an activator compound, and the curing of thesecond coating layer comprises activating a polymerization reactionand/or an addition reaction in the second coating layer with theactivator compound in the first coating layer. In this manner, theactivator compound in the first coating layer may initiatepolymerization reactions and/or Michael addition reactions in the secondcoating layer at the interface between the two layers. The activatorcompound in the first coating layer may also migrate through theinterface and into the second coating layer to further initiate curingreactions. In this example, the chemical composition of the firstcoating layer may be such that the activator does not function toinitiate crosslinking or other curing reactions in the first coatinglayer, but does so initiate curing reaction in the second coating layerupon application of the second coating layer over and in direct contactwith the first coating layer.

Alternatively, the second coating layer may comprise an activatorcompound, and the curing of the first coating layer comprises activatinga polymerization reaction and/or an addition reaction in the firstcoating layer with the activator compound in the second coating layer.In this manner, the activator compound in the second coating layer mayinitiate polymerization reactions and/or Michael addition reactions inthe first coating layer at the interface between the two layers. Theactivator compound in the second coating layer may also migrate throughthe interface and into the first coating layer to further initiatecuring reactions. In this example, the chemical composition of thesecond coating layer may be such that the activator does not function toinitiate crosslinking or other curing reactions in the second coatinglayer, but does so initiate curing reaction in the first coating layerupon application of the second coating layer over and in direct contactwith the first coating layer. The activator present in either the firstcoating layer or the second coating layer which initiates crosslinkingor other curing reactions in the other coating layer can comprise anactivator compound such as amine activator (e.g., a tertiary aminecompound such as DABCO or DMAE/DMEA).

In some examples, the first coating layer and/or the second coatinglayer can be applied over at least a portion of a bare substrate or apre-applied coating (e.g., a primer coating) using applicationtechniques such as spraying, electrostatic spraying, dipping, rolling,brushing, electrocoating, and the like. Once applied, the first coatinglayer and the second coating layer can be dehydrated and/or cured. Asdescribed above, the curing of the first coating layer and the secondcoating layer can be performed sequentially (i.e., the first coatinglayer is cured before the application of the second coating layer) orsimultaneously with or without intermediate flashing, drying, ordehydrating steps. For example, the first coating layer can be appliedand dehydrated, the second coating layer can be applied over thedehydrated first coating layer, and both the first and second coatinglayers baked or otherwise treated to cure the multi-layer system. Thespecific curing conditions of the coating layers will be based, at leastin part, on the chemical formulation of the curable composition formingthe layers. In some examples, the first coating layer and/or the secondcoating layer can be dehydrated and/or cured, independently or together,at temperatures ranging from ambient temperature (about 20° C. to 25°C.) to 500° C., or any sub-range subsumed therein, for example, fromambient temperatures to 200° C., from ambient temperatures to 150° C.,from ambient temperatures to 140° C., from ambient temperatures to 130°C., from ambient temperatures to 120° C., from ambient temperatures to100° C., from ambient temperatures to 90° C., from ambient temperaturesto 80° C., from ambient temperatures to 60° C., or from ambienttemperatures to 50° C.

As described above, 1,1-di-activated vinyl compounds and/ormultifunctional forms thereof can undergo polymerization reactions(e.g., anionic polymerization initiated by amines or other alkalineactivator compounds). Accordingly, after curing, at least one of thecured first coating layer and/or the cured second coating layer maycomprise a polymerization reaction product of a 1,1-di-activated vinylcompound and/or a multifunctional forms thereof. The 1,1-di-activatedvinyl compound and/or a multifunctional forms thereof may comprise adialkyl methylene malonate, a diaryl methylene malonate, amultifunctional form of a dialkyl methylene malonate, or amultifunctional form of a diaryl methylene malonate, or a combination ofany thereof.

Additionally, as described above, 1,1-di-activated vinyl compoundsand/or multifunctional forms thereof can function as crosslinking/curingagents for polyfunctional polymeric resins or polyfunctional monomericcompounds. Again not intending to be bound by any theory, it is believedthat the vinyl group(s) in the 1,1-di-activated vinyl compounds and/orthe multifunctional forms thereof can react via a Michael additionmechanism with the hydroxyl, amine, mercapto, and/or carbamate groups inpolyfunctional polymeric resins or polyfunctional monomeric compounds)and thereby form stable covalent linkages. Accordingly, after curing, atleast one of the cured first coating layer and/or the cured secondcoating layer may comprise a polymerization reaction product and anaddition reaction product of (1) a polyol, a polyamine, a polythiol, ora polycarbamate, or a combination of any thereof, and (2) a1,1-di-activated vinyl compound and/or a multifunctional forms thereof.The 1,1-di-activated vinyl compound and/or a multifunctional formsthereof may comprise a dialkyl methylene malonate, a diaryl methylenemalonate, a multifunctional form of a dialkyl methylene malonate, or amultifunctional form of a diaryl methylene malonate, or a combination ofany thereof.

In some examples, after curing, at least one of the cured first coatinglayer and/or the cured second coating layer may comprise apolymerization reaction product of a dialkyl methylene malonate and/or amultifunctional form of dialkyl methylene malonate. The multifunctionalform of the dialkyl methylene malonate may comprise atransesterification adduct of a dialkyl methylene malonate and at leastone polyol. The transesterification adduct of the dialkyl methylenemalonate and the at least one polyol may comprise a transesterificationadduct of the dialkyl methylene malonate and a diol (e.g., an alkanediol such as 1,5-pentanediol or 1,6-hexanediol). In some examples, aftercuring, at least one of the cured first coating layer and/or the curedsecond coating layer may also comprise an addition reaction product of(1) a polyol, a polyamine, a polythiol, or a polycarbamate, or acombination of any thereof, and (2) a dialkyl methylene malonate and amultifunctional form of a dialkyl methylene malonate. The dialkylmethylene malonate and/or the multifunctional form of the dialkylmethylene malonate may comprise, for example, dimethyl methylenemalonate (D3M) or diethyl methylene malonate (DEMM).

The invention described in this specification includes multi-layercoatings comprising a coating layer formed from the curable compositionsdescribed above. For example, a multi-layer coating can comprise a firstcoating layer applied over at least a portion of a substrate, and asecond coating layer applied over at least a portion of the firstcoating layer. The first coating layer and the second coating layer bothindependently comprise a polymeric resin. The first coating layer and/orthe second coating layer can comprise a polymerization reaction productof a 1,1-di-activated vinyl compound, or a multifunctional form thereof,or a combination thereof. The first coating layer and/or the secondcoating layer may further comprise an addition reaction product of (1) apolyol, a polyamine, a polythiol, or a polycarbamate, or a combinationof any thereof, and (2) a 1,1-di-activated vinyl compound, or amultifunctional form thereof, or a combination thereof.

In examples where only the first coating layer or the second coatinglayer is formed from a curable composition comprising a 1,1-di-activatedvinyl compound and/or a multifunctional form thereof (and optionally apolyfunctional resin or compound), the other coating layer can be formedfrom a different curable composition comprising any useful formulation.Other types of curable compositions than can be used with curablecompositions comprising a 1,1-di-activated vinyl compound, or amultifunctional form thereof, or a combination thereof to producemulti-layer coatings include, for example, polyurethane-based coatingcompositions, polyurea-based coating compositions, acrylic-based coatingcompositions, epoxy-based coating compositions, polyester-based coatingcompositions, polyether-based coating compositions, polythioether-basedcoating compositions, polyamide-based coating compositions,polycarbonate-based coating compositions, polycarbamate-based coatingcompositions, and aminoplast-based coating compositions (includingcoating compositions comprising urea-formaldehyde and/ormelamine-formaldehyde resins).

In some examples, the first coating layer comprises a thermoset resincomprising polyester resin, polyurethane resin, polyurea resin,polyether resin, polythioether resin, polycarbonate resin, polycarbamateresin, epoxy resin, phenolic resin, or aminoplast resin, or acombination of any thereof, and the second coating layer comprises apolymerization reaction product of a 1,1-di-activated vinyl compound, ora multifunctional form thereof, or a combination thereof. The secondcoating layer may comprise a clearcoat layer.

Curable composition comprising a 1,1-di-activated vinyl compound, or amultifunctional form thereof, or a combination thereof can be used toform basecoats, topcoats, tiecoats, and the like, in combination withother coating chemistries that form other coating layers in amulti-layer coating system. As used in this specification, the term“basecoat” means a coating layer that is deposited onto a primer and/ordirectly onto a substrate, optionally including components (such aspigments) that impact the color and/or provide other visual impact. Asused in this specification, the term “topcoat” means a coating layerthat is deposited over another coating layer such as a basecoat.Topcoats are often, but not always, “clearcoats,” which as used in thisspecification means a coating layer that is at least substantiallytransparent or fully transparent to visible. As used in thisspecification, the term “substantially transparent” refers to a coatingwherein a surface beyond the coating is at least partially visible tothe naked eye when viewed through the coating. As used in thisspecification, the term “fully transparent” refers to a coating whereina surface beyond the coating is completely visible to the naked eye whenviewed through the coating. It is appreciated that a clearcoat cancomprise colorants, such as pigments, provided that the colorants do notinterfere with the desired transparency of the clearcoat layer. In someexamples, a clearcoat layer is free of added colorants such as pigments.As used in this specification, the term “tiecoat” means a coating layerthat is located between two other coating layers, such as, for example,a coating layer located between a basecoat layer and a topcoat layer.

The multi-layer coatings described in this specification can comprise aprimer coating layer, which can correspond to a first coating layer. Asused in this specification, a “primer coating layer” means anundercoating that may be deposited onto a substrate in order to preparethe surface for application of a protective or decorative coatingsystem. A primer coating layer can be formed over at least a portion ofthe substrate as a first coating layer and a second coating layer (e.g.,a basecoat) can be formed over at least a portion of the primer coatinglayer. As such, the multi-layer coating of the present invention cancomprise a primer coating layer and one or more of a basecoat layer anda topcoat layer.

A first coating layer comprising a primer coating layer can be formedfrom a coating composition that comprises a film-forming resin such as acationic based resin, an anionic based resin, and/or any of theadditional film-forming resins previously described. The coatingcomposition used to form the primer coating composition can include acorrosion inhibitor, particularly in coating formulations intended foruse on metallic substrates. As used in this specification, a “corrosioninhibitor” means a component reduces the rate or severity of corrosionof a surface on a metal or metal alloy substrate. Also, the firstcoating layer can be a direct gloss coating. A direct gloss coating, inthis context, refers to a pigmented top coat layer is either glossy orhas a matte finish.

A corrosion inhibitor can include, but is not limited to, an alkalimetal component, an alkaline earth metal component, a transition metalcomponent, or combinations of any thereof. The term “alkali metal”refers to an element in Group 1 (International Union of Pure and AppliedChemistry (IUPAC)) of the periodic table of the chemical elements, andincludes, e.g., cesium (Cs), francium (Fr), lithium (Li), potassium (K),rubidium (Rb), and sodium (Na). The term “alkaline earth metal” refersto an element of Group 2 (IUPAC) of the periodic table of the chemicalelements, and includes, e.g., barium (Ba), beryllium (Be), calcium (Ca),magnesium (Mg), and strontium (Sr). The term “transition metal” refersto an element of Groups 3 through 12 (IUPAC) of the periodic table ofthe chemical elements, and includes, e.g., titanium (Ti), zirconium(Zr), chromium (Cr), and zinc (Zn), among various others. Examples ofinorganic components that can function as corrosion inhibitors in primercoating compositions include magnesium oxide, magnesium hydroxide,magnesium carbonate, magnesium phosphate, magnesium silicate, zincoxide, zinc hydroxide, zinc carbonate, zinc phosphate, zinc silicate,zinc dust, and combinations thereof.

The components of a primer coating composition can be selected to forman electrodepositable coating composition. As used in thisspecification, the term “electrodepositable coating composition” refersto a coating composition that is capable of being deposited onto anelectrically conductive substrate under the influence of an appliedelectrical potential. Examples of electrodepositable coatingcompositions include anionic and cationic electrodepositable coatingcompositions, such as epoxy or polyurethane-based coatings, such as theelectrodepositable coatings described in U.S. Pat. No. 4,933,056 atcolumn 2, line 48 to column 5, line 53; U.S. Pat. No. 5,530,043 atcolumn 1, line 54 to column 4, line 67; U.S. Pat. No. 5,760,107 atcolumn 2, line 11 to column 9, line 60; and U.S. Pat. No. 5,820,987 atcolumn 3, line 48 to column 10, line 63, each of which is incorporatedby reference into this specification. Suitable electrodepositablecoating compositions also include those commercially available from PPGIndustries, Inc., such as the POWERCRON® series of anodic and cathodicepoxy and acrylic coatings, ED-6060C, ED-6280, ED-6465, and ED-7000, forexample.

As described above, a primer coating composition can be deposited as afirst coating layer directly over at least a portion of a substratebefore application of a second coating layer. Alternatively, a firstcoating layer can be deposited over a cured primer coating layer wherethe first coating layer functions as a basecoat layer, and a secondcoating layer deposited over the first coating layer where the secondcoating layer functions as a topcoat layer or a tiecoat layer (when asubsequent layer is applied over the second coating layer). Once aprimer coating composition is applied to at least a portion of asubstrate, the primer coating layer can be dehydrated and/or curedbefore applying an overcoating layer, whether a basecoat or a topcoat. Aprimer coating composition can be dehydrated and/or cured, for example,at a temperature of 175° C. to 205° C. to form a primer coating layer.

When a curable composition comprising a 1,1-di-activated vinyl compound,or a multifunctional form thereof, or a combination thereof is used toform a basecoat layer or a tiecoat layer, the multi-layer coating cancomprise a topcoat layer formed from a different curable compositionsuch as, for example a curable composition formulated to produce anisocyanate-crosslinked polyurethane clearcoat. Additional examples oftopcoat layers that can be used with the multi-layer coating of thepresent invention include those described in U.S. Pat. No. 4,650,718 atcolumn 1, line 62 to column 10, line 16; U.S. Pat. No. 5,814,410 atcolumn 2, line 23 to column 9 line 54; and U.S. Pat. No. 5,891,981 atcolumn 2, line 22 to column 12, line 37, each of which is incorporatedby reference into this specification. Suitable topcoat coatingcompositions that can be used to form a topcoat layer over the coatinglayers comprising reaction products of a 1,1-di-activated vinylcompound, or a multifunctional form thereof, or a combination thereof,also include those commercially available from PPG Industries, Inc.under the trademarks NCT®, DIAMOND COAT®, and CERAMICLEAR®.

As described above, in the multi-layer coatings of the presentinvention, at least one of the first coating layer and/or the secondcoating layer can comprise a polymerization reaction product of the1,1-di-activated vinyl compound, or a multifunctional form thereof, or acombination thereof. The first coating layer and/or the second coatinglayer can further comprise an addition reaction product of: (1) apolyol, a polyamine, a polythiol, or a polycarbamate, or a combinationof any thereof and (2) a 1,1-di-activated vinyl compound, or amultifunctional form thereof, or a combination thereof. As described,the 1,1-di-activated vinyl compound can comprise, for example, amethylene dicarbonyl compound, a dihalo vinyl compound, a dihaloalkyldisubstituted vinyl compound, or a cyanoacrylate compound, or amultifunctional form of any thereof, or a combination of any thereof.

In some examples of the multi-layer coating, the first coating layerand/or the second coating layer can comprise a polymerization reactionproduct of a dialkyl methylene malonate, a diaryl methylene malonate, amultifunctional form of a dialkyl methylene malonate, or amultifunctional form of a diaryl methylene malonate, or a combination ofany thereof. For instance, the first coating layer and/or the secondcoating layer can comprise a polymerization reaction product of diethylmethylene malonate and a multifunctional form of diethyl methylenemalonate. The multifunctional form of diethyl methylene malonate cancomprise a transesterification adduct of diethyl methylene malonate andat least one polyol. The transesterification adduct of the diethylmethylene malonate and the at least one polyol can comprise atransesterification adduct of diethyl methylene malonate and a diol(e.g., an alkane diol such as 1,5-pentanediol or 1,6-hexanediol).

In some examples of the multi-layer coating, the first coating layerand/or the second coating layer can be formed from a curable compositionincluding a promoter (e.g., a strong acid such as a sulfonic acid and/ora heteropoly acid) and/or an activator (e.g., an amine such as atertiary amine like DABCO or DMAE/DMEA, or an ionic liquid) and/or anextender (e.g., an anhydride-containing vinyl polymer). In someexamples, the first coating layer comprises an activator compound thatactivated polymerization reactions in the second coating layer when thesecond coating layer was applied over the first coating layer. In otherexamples, the second coating layer comprises an activator compound thatactivated polymerization reactions in the first coating layer when thesecond coating layer was applied over the first coating layer.

In some examples, the second coating layer comprises a polymerizationreaction product of the 1,1-di-activated vinyl compound and/ormultifunctional form thereof (and optionally an addition reactionproduct of a polyfunctional resin or polyfunctional compound and the1,1-di-activated vinyl compound and/or multifunctional form thereof),and the first coating layer is formed from a curable composition thatcures when heated at a temperature of less than 500° C., less than 200°C., less than 150° C., less than 140° C., less than 130° C., less than120° C., or less than 100° C. The curable composition that forms thefirst coating layer can comprise, for example, polyurethane-basedcoating compositions, polyurea-based coating compositions, acrylic-basedcoating compositions, epoxy-based coating compositions, polyester-basedcoating compositions, polyether-based coating compositions,polythioether-based coating compositions, polyamide-based coatingcompositions, polycarbonate-based coating compositions,polycarbamate-based coating compositions, and aminoplast-based coatingcompositions (including coating compositions comprisingurea-formaldehyde and/or melamine-formaldehyde resins). In someexamples, the first coating layer is formed from a curable compositionthat does not comprise (i.e., is substantially free of) melamine resinand formaldehyde condensates. The term “substantially free,” as used inthis specification, means that the described materials are present, ifat all, at incidental impurity levels, generally less than 1000 partsper million (ppm) by weight based on total curable composition weight.

In some examples, the first coating layer comprises a polymerizationreaction product of the 1,1-di-activated vinyl compound and/ormultifunctional form thereof (and optionally an addition reactionproduct of the polyfunctional resin or polyfunctional compound and the1,1-di-activated vinyl compound and/or multifunctional form thereof),and the second coating layer comprises a clearcoat layer (e.g., anisocyanate-crosslinked polyurethane clearcoat layer).

In some examples, the first coating layer comprises a polymerizationreaction product of the 1,1-di-activated vinyl compound and/ormultifunctional form thereof (and optionally an addition reactionproduct of the polyfunctional resin or polyfunctional compound and the1,1-di-activated vinyl compound and/or multifunctional form thereof),wherein the first coating layer is applied directly onto a metallicsubstrate. The first coating layer applied directly onto a metallicsubstrate may further comprise a wetting agent. For example, the firstcoating layer applied directly onto a metallic substrate may furthercomprise a polysiloxane-based wetting agent, such as, for example, apolyether-modified polydimethylsiloxane (e.g., poly(ethyleneoxide)-polydimethylsiloxane and/or poly(propyleneoxide)-polydimethylsiloxane).

The multi-layer coatings can be applied to a wide range of substratesincluding vehicle components and components of free-standing structuressuch as buildings, bridges, or other civil infrastructures. Morespecific substrates include, but are not limited to, automotivesubstrates (e.g., body panels and other parts and components),industrial substrates, aircraft components, watercraft components,packaging substrates (e.g., food and beverage cans), wood flooring andfurniture, apparel, electronics (e.g., housings and circuit boards),glass and transparencies, sports equipment (e.g., golf balls, and thelike), appliances (e.g., dish washing machines, clothes washingmachines, clothes drying machines). Substrates can be, for example,metallic or non-metallic. Metallic substrates include, but are notlimited to, tin, steel (including electrogalvanized steel, cold rolledsteel, hot-dipped galvanized steel, among others), aluminum, aluminumalloys, zinc-aluminum alloys, steel coated with a zinc-aluminum alloy,and aluminum plated steel. Non-metallic substrates include polymeric,plastic, polyester, polyolefin, polyamide, cellulosic, polystyrene,polyacrylic, poly(ethylene naphthalate), polypropylene, polyethylene,nylon, EVOH, polylactic acid, other “green” polymeric substrates,poly(ethyleneterephthalate) (PET), polycarbonate, polycarbonateacrylobutadiene styrene (PC/ABS), polyamide, wood, veneer, woodcomposite, particle board, fiberboard, cement, concrete, brick, stone,paper, cardboard, textiles, leather (both synthetic and natural), glassor fiberglass composites, carbon fiber composites, mixed fiber (e.g.,fiberglass and carbon fiber) composites, and the like. The substrate canbe one that has been already treated in some manner, such as to impartvisual and/or color effect, a protective pretreatment or primer coatinglayer, or other coating layer, and the like.

The present invention further provides an article comprising themulti-layer coatings formed from the curable compositions described inthis specification. For example, the multi-layer coatings of the presentinvention are also suitable for use as packaging coatings. Theapplication of various pretreatments and coatings to packaging is wellestablished. Such treatments and/or coatings, for example, can be usedin the case of metal cans, wherein the treatment and/or coating is usedto retard or inhibit corrosion, provide a decorative coating, provideease of handling during the manufacturing process, and the like.Coatings can be applied to the interior of such cans to prevent thecontents from contacting the metal of the container. The coatingsapplied to the interior of metal cans also help prevent corrosion in theheadspace of the cans, which is the area between the fill line of theproduct and the can lid; corrosion in the headspace is particularlyproblematic with food products having a high salt content. Coatings canalso be applied to the exterior of metal cans. Certain coatings of thepresent invention are particularly applicable for use with coiled metalstock, such as the coiled metal stock from which the ends of cans aremade (“can end stock”), and end caps and closures are made (“cap/closurestock”). Since coatings designed for use on can end stock andcap/closure stock are typically applied prior to the piece being cut andstamped out of the coiled metal stock, they are typically flexible andextensible. Coatings for cans subjected to relatively stringenttemperature and/or pressure requirements should also be resistant topopping, corrosion, blushing and/or blistering.

Accordingly, the present invention is further directed to a packagecoated at least in part with any of the multi-layer coatings describedabove. A “package” is anything used to contain another item,particularly for shipping from a point of manufacture to a consumer, andfor subsequent storage by a consumer. A package will be thereforeunderstood as something that is sealed so as to keep its contents freefrom deterioration until opened by a consumer. Thus, the present“package” is distinguished from a storage container or bakeware in whicha consumer might make and/or store food; such a container would onlymaintain the freshness or integrity of the food item for a relativelyshort period. A package according to the present invention can be madeof metal or non-metal, for example, plastic or laminate, and be in anyform. An example of a suitable package is a laminate tube. Anotherexample of a suitable package is a metal can. The term “metal can”includes any type of metal can, container, or any type of receptacle orportion thereof that is sealed by the food/beverage manufacturer tominimize or eliminate spoilage of the contents until such package isopened by the consumer. One example of a metal can is a food can;

the term “food can(s)” is used herein to refer to cans, containers orany type of receptacle or portion thereof used to hold any type of foodand/or beverage. The term “metal can(s)” specifically includes food cansand also specifically includes “can ends” including “easy open ends,”which are typically stamped from can end stock and used in conjunctionwith the packaging of food and beverages. The term “metal cans” alsospecifically includes metal caps and/or closures such as bottle caps,screw top caps and lids of any size, lug caps, and the like. The metalcans can be used to hold other items as well, including, but not limitedto, personal care products, bug spray, spray paint, and any othercompound suitable for packaging in an aerosol can. The cans can include“two piece cans” and “three-piece cans” as well as drawn and ironedone-piece cans; such one piece cans often find application with aerosolproducts. Packages coated according to the present invention can alsoinclude plastic bottles, plastic tubes, laminates and flexiblepackaging, such as those made from PE, PP, PET and the like. Suchpackaging could hold, for example, food, toothpaste, personal careproducts and the like. The coating can be applied to the interior and/orthe exterior of the package.

In some examples, the multi-layer coatings prepared and used accordingto the present invention may be substantially free, may be essentiallyfree, and/or may be completely free of bisphenol A and epoxy compoundsderived from bisphenol A (“BPA”), such as bisphenol A diglycidyl ether(“BADGE”). The term “substantially free” as used in this context meansthe coatings compositions contain less than 1000 parts per million(ppm), “essentially free” means less than 100 ppm, and “completely free”means less than 20 parts per billion (ppb) of any of the above mentionedcompounds, derivatives, or residues thereof.

WORKING EXAMPLES

The following working examples are intended to further describe theinvention. It is understood that the invention described in thisspecification is not necessarily limited to the examples described inthis section. In particular, the curable compositions of the disclosuremay take various forms, including sealants, coatings, adhesives,encapsulants, and potting compositions, as set forth is some of thefollowing examples presented herein.

Example 1A: Coating Layer Comprising 1,1-Di-Activated Vinyl CompoundPolymerization Product on Metallic Substrate

A 1,1-di-activated vinyl compound (dimethyl methylene malonate) and apolyether-modified polydimethylsiloxane (BYK-333, available fromBYK-Chemie GmbH) were added to a 20 milliliter glass vial and stirredunder ambient conditions until homogeneous. The dimethyl methylenemalonate and the polyether-modified polydimethylsiloxane were combinedtogether in the amounts provided in Table 1 to form a liquid coatingcomposition.

TABLE 1 Component Part by weight (grams) D3M¹ 99 BYK-333² 1 ¹Dimethylmethylene malonate. ²Polyether-modified polydimethylsiloxane availablefrom BYK-Chemie GmbH.

The liquid coating composition was applied directly onto a 4-inch by12-inch hot-dipped galvanized steel panel (available form ACT TestPanels LLC) using a 1.4 mil wire-round drawdown bar to form a coatinglayer. The coating layer was tested for film drying and curingproperties. Tack-free time was measured as the amount of time requiredfor an applied coating film to achieve a level of dryness, such that,upon the application and removal of a cotton ball, no cotton fibers weretransferred to the coating surface. The cotton ball was applied in thefollowing manner:

-   -   1. With the substrate panel in a horizontal position, hold a        cotton ball approximately 3 inches above and drop the cotton        ball onto the applied coating film.    -   2. Hold the substrate panel coating side up for 5±2 seconds with        the cotton ball in contact with the coating film.    -   3. After the 5±2 seconds, flip the substrate panel coating side        down.        -   a. If the cotton ball drops off leaving no fibers on the            film, the coating is tack-free.        -   b. If the cotton ball does not drop off or leaves fibers,            repeat steps 1-3 at appropriate time intervals (e.g., every            15 minutes) until coating is tack-free.            The coating layer reached a tack-free state under ambient            conditions at a point in time between 15 and 30 minutes            after application to the steel panel.

An MEK double rub test was also performed. The MEK double rub testreports the number of double (back-and-forth) rubs, performed by handwith a methyl ethyl ketone (MEK) soaked rag, required to dissolve theapplied coating such that the substrate is visible. This MEK double rubtest was performed after about 24 hours under ambient conditionsmeasured from the time of coating application. The double rubs wereperformed up to a maximum number of 100 and discontinued. The coatinglayer survived the 100 MEK double rubs with no visible damage.

The relatively rapid drying of the applied coating layer and developmentof MEK solvent resistance indicated that a polymerized and crosslinkedfilm was formed having good intra-film cohesion and adhesion to theunderlying steel substrate.

Example 1B: Coating Layer Comprising a 1,1-Di-Activated Vinyl CompoundPolymerization Product on Metallic Substrate

A 1,1-di-activated vinyl compound (dimethyl methylene malonate) and apolyether-modified polydimethylsiloxane (BYK-333, available fromBYK-Chemie GmbH) were added to a 20 milliliter glass vial and stirredunder ambient conditions until homogeneous. The dimethyl methylenemalonate and the polyether-modified polydimethylsiloxane were combinedtogether in the amounts provided in Table 2 to form a liquid coatingcomposition.

TABLE 2 Component Part by weight (grams) D3M¹ 99 BYK-333² 1 ¹Dimethylmethylene malonate. ²Polyether-modified polydimethylsiloxane availablefrom BYK-Chemie GmbH.

The liquid coating composition was applied directly onto a 4-inch by12-inch electrogalvanized steel panel (available form ACT Test PanelsLLC) using a 1.4 mil wire-round drawdown bar to form a coating layer.The coating layer was tested for film drying and curing properties.Tack-free time was measured as described above in Example 1A. Thecoating layer reached a tack-free state under ambient conditions at apoint in time between 15 and 30 minutes after application to the steelpanel. An MEK double rub test was also performed as described above inExample 1A (after about 24 hours under ambient conditions measured fromthe time of coating application). The coating layer survived the 100 MEKdouble rubs with no visible damage.

The relatively rapid drying of the applied coating layer and developmentof MEK solvent resistance indicated that a polymerized and crosslinkedfilm was formed having good intra-film cohesion and adhesion to theunderlying steel substrate.

Example 1C: Coating Layer Comprising a 1,1-Di-Activated Vinyl CompoundPolymerization Product on Metallic Substrate

A 1,1-di-activated vinyl compound (dimethyl methylene malonate) and apolyether-modified polydimethylsiloxane (BYK-333, available fromBYK-Chemie GmbH) were added to a 20 milliliter glass vial and stirredunder ambient conditions until homogeneous. The dimethyl methylenemalonate and the polyether-modified polydimethylsiloxane were combinedtogether in the amounts provided in Table 3 to form a liquid coatingcomposition.

TABLE 3 Component Part by weight (grams) D3M¹ 99 BYK-333² 1 ¹Dimethylmethylene malonate. ²Polyether-modified polydimethylsiloxane availablefrom BYK-Chemie GmbH.

The liquid coating composition was applied directly onto a 4-inch by12-inch 6022 aluminum alloy panel (available form ACT Test Panels LLC)using a 1.4 mil wire-round drawdown bar to form a coating layer. Thecoating layer was tested for film drying and curing properties.Tack-free time was measured as described above in Example 1A. Thecoating layer reached a tack-free state under ambient conditions at apoint in time between 15 and 30 minutes after application to thealuminum alloy panel. An MEK double rub test was also performed asdescribed above in Example 1A (after about 24 hours under ambientconditions measured from the time of coating application). The coatinglayer survived the 100 MEK double rubs with no visible damage.

The relatively rapid drying of the applied coating layer and developmentof MEK solvent resistance indicated that a polymerized and crosslinkedfilm was formed having good intra-film cohesion and adhesion to theunderlying aluminum alloy substrate.

Example 2: Multi-Layer Coating System Comprising 1,1-Di-Activated VinylCompound Polymerization Product

A pigmented water-borne basecoating composition (Envirobase HighPerformance T409 (Black), available from PPG Industries, Inc.) wasapplied over a 4-inch by 12-inch cold-rolled steel substrate panelpre-coated with ED-6060C electrocoat (electrocoat available from PPGIndustries, Inc., and substrate panels available in pre-coated form fromACT Test Panels LLC). The basecoat layer was applied under ambientconditions by drawdown over the electrocoat on the substrate panel usinga drawdown bar with a 1 mil gap. The applied basecoat layer was allowedto dry for about 10-15 minutes under ambient conditions until a matteappearance was observed.

A second coating composition was immediately applied over the driedbasecoat layer to form a second coating layer. The second coatingcomposition comprised a combination of a 1,1-di-activated vinyl compoundand a multifunctional form thereof (a mixture of diethyl methylenemalonate and a transesterification adduct of diethyl methylene malonateand 1,6-hexanediol, as described in U.S. Publication No. 2014/0329980).The second coating layer was applied under ambient conditions bydrawdown over the dried basecoat layer using a drawdown bar with a 3 milgap. The second coating layer remained visibly glossy and developed atack-free state under ambient conditions within 5 minutes of applicationover the basecoat layer (measured using the cotton ball method describedabove in Example 1A). An MEK double rub test was also performed, asdescribed above in Example 1A, immediately after reaching the tack-freestate (about 5 minutes after application of the second coating layer).The second coating layer survived the 100 MEK double rubs with novisible damage.

Prior to the application of the second coating layer, the second coatingcomposition exhibited a water-like viscosity and only gelled when theliquid contacted the underlying basecoat layer. Without intending to bebound by any theory, it is believed that residual amine in the driedbasecoat layer functioned as an activator compound that activatedanionic polymerization of the diethyl methylene malonate and thetransesterification adduct of diethyl methylene malonate and1,6-hexanediol in the second coating layer.

Example 3: Multi-Layer Coating System Comprising 1,1-Di-Activated VinylCompound Polymerization Product

A coating composition comprising a combination of a 1,1-di-activatedvinyl compound and a multifunctional form thereof (a mixture of diethylmethylene malonate and a transesterification adduct of diethyl methylenemalonate and 1,6-hexanediol, as described in U.S. Publication No.2014/0329980) was applied over a 4-inch by 12-inch cold-rolled steelsubstrate panel pre-coated with ED-6060C electrocoat (electrocoatavailable from PPG Industries, Inc., and substrate panels available inpre-coated form from ACT Test Panels LLC). The coating layer was appliedunder ambient conditions by drawdown over the electrocoat on thesubstrate panel using a drawdown bar with a 3 mil gap. The coatingcomposition exhibited a water-like viscosity and did not gel when theliquid contacted the underlying electrocoat layer.

Eight (8) grams of an activator solution of1,4-diazabicyclo[2.2.2]octane (DABCO) in n-butyl acetate (0.3% solutionby weight) was spray applied over the coating layer using a SATA Jet4000 B HVLP with a 1.3 mm nozzle at 10 psi. The coating layer developeda tack-free state immediately upon spraying the activator solution(measured using the cotton ball method described above in Example 1A).An MEK double rub test was also performed, as described above in Example1A, within 5 minutes of the spraying of the activator solution. Thecoating layer survived the 100 MEK double rubs with no visible damage.

As described above, before and after the application of the coatinglayer, the coating composition exhibited a water-like viscosity and onlygelled when the activator solution was sprayed over the applied coatinglayer. Without intending to be bound by any theory, it is believed thatthe coating layer did not gel upon application because the fully-curedelectrocoat on the substrate panel either (1) did not contain anyresidual amine or other alkaline compounds to activate anionicpolymerization of the diethyl methylene malonate and thetransesterification adduct of diethyl methylene malonate and1,6-hexanediol in the second coating layer or (2) any residual amine orother alkaline compounds were insufficiently mobile, possibly due to thecrosslinked state of the binder resin in the electrocoat, to migrate tothe surface of the cured electrocoat or otherwise contact the coatinglayer applied over the electrocoat. It is expected, however, thatelectrodeposited coating compositions containing amine or other alkalinecompounds could activate anionic polymerization in coating compositionscomprising 1,1-di-activated vinyl compounds and/or multifunctional formsthereof applied over such electrodeposited coating layers before curingof the electrodeposited coating layers.

Example 4A: Multi-Layer Coating System Comprising 1,1-Di-Activated VinylCompound Polymerization Product

A water-borne basecoat system comprising two coating layers was appliedover a 4-inch by 12-inch cold-rolled steel substrate panel pre-coatedwith ED-6465 electrocoat (electrocoat available from PPG Industries,Inc., and substrate panels available in pre-coated form from ACT TestPanels LLC). The coating layers were applied under controlled conditionsof 20-22° C. temperature and 60-65% relative humidity. The first coatinglayer of the basecoat system (Basecoat A, described below) was sprayedover the electrocoat on the substrate panel using a Binks model 95ARConventional Air Spray Gun with a 1.8 millimeter nozzle at 60 psi. Thefirst coating layer of the basecoat system was allowed to dry for 5minutes under ambient conditions.

Basecoat A was a red pigmented basecoat composition, suitable for use asthe first basecoat layer in a multi-layer coating system, prepared inthe following manner. Components 1-9 listed in Table 4 below were mixedunder stirring to form an aqueous phase mixture. The red tint (Component10) and the white tint (Component 11) were then added to the aqueousphase mixture. Components 12-18 were mixed to form an organic phasemixture and stirred for 15 minutes before being added to the aqueousphase mixture. After mixing the aqueous and organic phase mixturestogether, the pH of the combined mixture was adjusted to 8.6 using 50%aqueous dimethylethanolamine. The resulting Basecoat A composition wasaged for 24 hours under ambient conditions before viscosity adjustmentwith demineralized water. The high shear viscosity of the Basecoat Acomposition was adjusted to 95 cps at 1000 sec-1 using a Brookfield CAP2000 viscometer with spindle #1.

TABLE 4 No. Component Parts by weight Aqueous Phase Components 1Polyester A ¹ 496.3 2 Latex A ² 439.2 3 Latex B ³ 577.0 4 Demineralizedwater 107.0 5 Dimethylethanolamine 1.2 6 Byk 348 ⁴ 2.2 7 Byk 032 ⁵ 16.48 2-ethylhexanol 158.6 9 Mineral spirits 36.5 10 Red tint paste ⁶ 1270.211 White tint paste ⁷ 3.6 Organic Phase Ingredients 12 Urethane diol ⁸82.8 13 Resimene HM2608 ⁹ 115.1 14 Cymel 1158 ¹⁰ 70.5 15 Polyester B ¹¹46.1 16 2-ethylhexanol 23.7 17 Ethylene glycol monobutyl ether 77.1 18Propylene glycol monobutyl ether 66.4 ¹ Polyester A was made with 73parts-by-weight of Empol 1008, 2.6 parts-by-weight of trimelliticanhydride, 5.2 parts-by-weight of dimethylol propionic acid, and 19.1parts-by-weight of 1,4 cyclohexane dimethanol, and had a weight averagemolecular weight (Mw) of 24,160 as measured by GPC, an acid value of15.5, and a solids content of 20% in water. ² Latex A was made with 4.1parts-by-weight dimethylethanolamine, 3.9 parts-by-weight hexanedioldiacrylate, 9.7 parts-by-weight 2-ethylhexyl acrylate, 24.9parts-by-weight methyl methacrylate, 5.9 parts-by-weight dimethylolpropionic acid, 5.8 parts-by-weight hydroxyethyl methacrylate, 29.5parts-by-weight polytetramethylene ether glycol (Mw = 1000), and 16.4parts-by-weight isophorone diisocyanate, and had a solids content of37.8% in water. ³ Latex B was made with 0.2 parts-by-weight dimethylethanolamine, 8.8 parts-by-weight acrylamide, 63 parts-by-weight butylacrylate, 25 parts-by-weight hexanediol diacrylate, 2 parts-by-weightmethyl methacrylate, and 1 part-by-weight butyl acrylate, and had asolids content of 31% in water. ⁴ Commercially available from BykChemie. ⁵ Commercially available from Byk Chemie. ⁶ Pigment dispersionas described in comparative Example 1 of U.S. Pat. No. 9,040,621. ⁷White tint paste comprising 61% TiO₂ dispersed in 9% acrylic polymerblend, and having a solids of 70%. ⁸ The urethane diol was made with70.1 parts-by-weight of polyoxypropylene diamine (Mw = 400) and 29.9parts-by-weight of ethylene carbonate. ⁹ Commercially available fromIneos Melamines. ¹⁰ Commercially available from Allnex. ¹¹ Polyester Bwas made with 39.2 parts-by-weight isostearic acid, 23.8 parts-by-weightcyclohexane dicarboxylic acid, 37 parts-by-weight trimethylol propane,and had a number average molecular weight (Mn) of 726 (determined by gelpermeation chromatography) and an acid value of 2 (determined bytitration), and had a solids content of 90% in xylene.

The second coating layer of the basecoat system (Basecoat B) was sprayedover the dried first coating layer of the basecoat system using a Binksmodel 95AR Conventional Air Spray Gun with a 1.8 millimeter nozzle at 60psi. The second coating layer was sprayed in two consecutive coatswithout any intermediate drying between spray applications. The twocoating layers of the basecoat system where then allowed to dry for 5minutes under ambient conditions and thereafter dehydrated for 7 minutesat 70° C. The film thickness of the basecoat system (both coatinglayers) after dehydrating was approximately 34-40 micrometers.

Basecoat B was a metallic red pigmented basecoat composition, suitablefor use as the second basecoat layer in a multi-layer coating system,prepared in the following manner. Components 1-12 listed in Table 5below were mixed under stirring to form an aqueous phase mixture.Components 13 and 14 were then mixed separately for about 20 minutesuntil the mixture was clear and then added to the rest of the aqueousphase components under stirring. Components 15-18 were mixed to form anorganic phase mixture and stirred for 15 minutes prior to being added tothe aqueous phase mixture. After mixing the aqueous and organic phasemixtures together, the pH of the combined mixture was adjusted to 8.8using 50% dimethylethanolamine. The resulting Basecoat B composition wasaged for 24 hours under ambient conditions before viscosity adjustmentwith demineralized water. The high shear viscosity of the Basecoat Bcomposition was adjusted to 80 cps at 1000 sec-1 using a Brookfield CAP2000 viscometer with spindle #1

TABLE 5 No. Components Parts by weight Aqueous Phase Ingredients 1Polyester A 643.6 2 Latex A 450.7 3 Latex C ¹ 290.0 4 Demineralizedwater 86.7 5 Dimethylethanolamine 3.5 6 Byk 348 1.46 7 Byk 032 15.56 82-ethylhexanol 80.3 9 Propylene glycol monobutyl ether 76.4 10 Mineralspirits 119.7 11 Red tint paste 518.3 12 Svnolox 100-D45 ² 15.8 13Demineralized water 583.9 14 Laponite RD ³ 11.7 Organic PhaseIngredients 15 Resimene HM2608 221.5 16 Aluminium paste ⁴ 153.1 17Polyester B 45.0 18 Propylene glycol monobutyl ether 141.6 ¹ Latex C wasmade with 8.8 parts-by-weight of 50% acrylamide, 63 parts-by-weightn-butyl methacrylate, 25.6 parts-by-weight 1,6-hexanediol diacrylate,1.7 parts-by-weight methyl methacrylate, 0.9 parts-by-weight n-butylacrylate, and had a solids content of 25% in water. ² Polypropyleneglycol available from Dow Chemical. ³ Sodium lithium magnesium silicateavailable from Southern Clay Products. ⁴ TSB 2180A aluminum pasteavailable from Toyal America.

A third coating composition was immediately applied over the dehydratedbasecoat system to form a third coating layer. The third coatingcomposition comprised a combination of a 1,1-di-activated vinyl compoundand a multifunctional form thereof (a mixture of diethyl methylenemalonate and a transesterification adduct of diethyl methylene malonateand 1,6-hexanediol, as described in U.S. Publication No. 2014/0329980).The third coating layer was applied under ambient conditions by drawdownover the dehydrated basecoat layers using a drawdown bar with a 2 milgap. The substrate panel comprising the two-layer basecoat system andthe overlying third coating layer was dried under ambient conditions for10 minutes. Within 10 minutes of application, the third coating layerreached a tack-free state (measured using the cotton ball methoddescribed above in Example 1A).

After the 10 minute flash dry under ambient conditions, the substratepanel comprising the two-layer basecoat system and the overlying thirdcoating layer was baked for 30 minutes at 150° C. to cure the two-layerbasecoat system. An MEK double rub test was performed, as describedabove in Example 1A, on the cured multi-layer coating system. The thirdcoating layer (i.e., the topmost layer of the multi-layer coatingsystem) survived the 100 MEK double rubs with no visible damage ordecrease in visible gloss.

Prior to the application of the third coating layer, the third coatingcomposition exhibited a water-like viscosity and only gelled when theliquid contacted the underlying basecoat layers. Without intending to bebound by any theory, it is believed that residual dimethylethanolaminein the dried basecoat layers functioned as an activator compound thatactivated anionic polymerization of the diethyl methylene malonate andthe transesterification adduct of diethyl methylene malonate and1,6-hexanediol in the second coating layer.

Example 4B: Comparative Multi-Layer Coating System

Example 4A was repeated but the two-layer basecoat system was baked andcured before application of the third coating layer. More specifically,a water-borne basecoat system comprising two coating layers was appliedover a 4-inch by 12-inch cold-rolled steel substrate panel pre-coatedwith ED-6465 electrocoat (electrocoat available from PPG Industries,Inc., and substrate panels available in pre-coated form from ACT TestPanels LLC). The coating layers were applied under controlled conditionsof 20-22° C. temperature and 60-65% relative humidity. The first coatinglayer of the basecoat system (Basecoat A from Example 4A) was sprayedover the electrocoat on the substrate panel using a Binks Model 95ARConventional Air Spray Gun with a 1.8 millimeter nozzle at 60 psi. Thefirst coating layer of the basecoat system was allowed to dry for 5minutes under ambient conditions.

The second coating layer of the basecoat system (Basecoat B from Example4A) was sprayed over the dried first coating layer of the basecoatsystem using a Binks Model 95AR Conventional Air Spray Gun with a 1.8millimeter nozzle at 60 psi. The second coating layer was sprayed in twoconsecutive coats without any intermediate drying between sprayapplications. The two coating layers of the basecoat system where thenallowed to dry for 5 minutes under ambient conditions and thereafterdehydrated for 7 minutes at 70° C. The film thickness of the basecoatsystem (both coating layers) after dehydrating was approximately 34-40micrometers. After the seven minute dehydration, the substrate panelcomprising the two-layer basecoat system was baked for 30 minutes at150° C. to cure the two-layer basecoat system.

A third coating composition was applied over the cured basecoat systemto form a third coating layer. The third coating composition comprised acombination of a 1,1-di-activated vinyl compound and a multifunctionalform thereof (a mixture of diethyl methylene malonate and atransesterification adduct of diethyl methylene malonate and1,6-hexanediol, as described in U.S. Publication No. 2014/0329980). Thethird coating layer was applied under ambient conditions by drawdownover the cured basecoat layers using a drawdown bar with a 2 mil gap.The third coating layer did not gel and remained in a liquid stateindefinitely after application to the cured basecoat system.

Without intending to be bound by any theory, it is believed that duringthe 30 minute, 150° C. bake to cure the two-layer basecoat system, thedimethylethanolamine in the basecoat layers likely volatilized andevaporated from the basecoat system. Additionally, any residualdimethylethanolamine present in the cured basecoat system after the bakewas either (1) present in insufficient quantities to activate anionicpolymerization of the diethyl methylene malonate and thetransesterification adduct of diethyl methylene malonate and1,6-hexanediol in the third coating layer or (2) insufficiently mobile,possibly due to the crosslinked state of the binder resin in the system,to migrate to the surface of the cured basecoat system or otherwisecontact the subsequently applied third coating layer. Thus, the curing(crosslinking) of the basecoat system before the application of thethird coating layer prevented the dimethylethanolamine in thebasecoating compositions from functioning as an activator compound toactivate anionic polymerization of the diethyl methylene malonate andthe transesterification adduct of diethyl methylene malonate and1,6-hexanediol in the third coating layer.

Example 5A: Multi-Layer Coating System Comprising 1,1-Di-Activated VinylCompound Polymerization Product

A low-temperature cure basecoat was applied over 4-inch by 12-inchcold-rolled steel substrate panels pre-coated with ED-6465 electrocoat(electrocoat available from PPG Industries, Inc., and substrate panelsavailable in pre-coated form from ACT Test Panels LLC). The basecoatcomposition was prepared with the components listed in Table 6.

TABLE 6 Component Part by weight (grams) Latex ¹ 196.62 Adipic aciddihydrazide 2.41 CARBODILITE ® V-02-L2 ² 9.88 Black tint ³ 50.48 Redtint ⁴ 15.95 BYK ® 348 ⁵ 0.43 BYK ® 032 ⁶ 1.73 BYKETOL ® WS ⁷ 11.12SURFYNOL ® 104E ⁸ 11.38 Deionized water 53.00 ¹ Described below. ²Waterborne carbodiimide crosslinker with a hydrophilic segment,commercially available from GSI Exim America, Inc. ³ Black tint pasteconsisting of 6% carbon black dispersed in 15% acrylic polymer andhaving a solids content of 22%. ⁴ Red tint paste consisting of 13%transparent iron oxide red dispersed in 13% acrylic polymer and having asolids content of 27%. ⁵ Polyether modified siloxane, available fromBYK-Chemie GmbH. ⁶ Emulsion of paraffin-based mineral oils andhydrophobic components, available from BYK-Chemie GmbH. ⁷ Silicone-freesurface additive, available from BYK-Chemie GmbH. ⁸ Surfactant,available from Air Products and Chemicals, Inc.

The basecoat composition was prepared by mixing the components listed inTable 6 with a conventional stir blade while preventing foaming and airentrapment. The latex component was prepared beforehand as follows:

First, a polyurethane was prepared by charging the components listed inTable 7 into a four necked round bottom flask fitted with athermocouple, mechanical stirrer, and condenser.

TABLE 7 Component Part by weight (grams) butyl acrylate 538 FOMREZ ®66-56 ¹ 433 POLYMEG ® 2000 polyol ² 433 2,6-di-tert-butyl 4-methylphenol 3.1 hydroxyethyl methacrylate (HEMA) 41.4 dimethylol propionicacid (DMPA) 140 triethylamine 6.3 ¹ Hydroxyl-terminated, saturatedlinear polyester polyol, available from Chemtura Corp. ²Polytetramethylene ether glycol, available from LyondellBasellIndustries N.V.

The mixture was heated to 50° C. and held for 15 minutes. Next, 601.0parts-by-weight (grams) of isophorone diisocyanate was charged into theflask over 10 minutes, and mixed for 15 minutes. After mixing, 39parts-by-weight (grams) of butyl acrylate and 1.6 parts-by-weight(grams) of dibutyl tin dilaurate (DBTDL) was charged into the flask andimmediate exotherm was observed. After exotherm subsided, the mixturewas heated to 90° C. and held for 60 minutes. The mixture was cooled to70° C. and 538 grams of butyl acrylate and 94.0 grams of hexanedioldiacrylate were charged into the flask. The resulting mixture was keptat 60° C. before being dispersed into water and then allowed to cool toambient temperature to provide the polyurethane product.

The polyurethane product was used to produce the latex. The latexcomprised polyurethane-acrylic shell-core particles with urea linkages,urethane linkages, pendant carboxylic acid functionality, and pendantketo functionality on the polyurethane shell. The latex was prepared bycharging the components listed in Table 8 into a four necked roundbottom flask fitted with a thermocouple, mechanical stirrer, andcondenser.

TABLE 8 Component Part by weight (grams) Deionized water 2400.0diacetone acrylamide 215 dimethyl ethanolamine 88 ethylenediamine 50The mixture was heated to 70° C. and held for two hours with an N₂blanket. After heating the mixture, 1925 parts-by-weight (grams) ofdeionized water and 40 parts-by-weight (grams) of AEROSOL® OT-75 (asurfactant, available from Cytec Solvay Group) were charged into theflask and held at 50° C. for 15 minutes. Next, 2600.0 parts-by-weight(grams) of the polyurethane product described above was dispersed intothe flask over 20 minutes and mixed for an additional 15 minutes. Amixture of 7.7 parts-by-weight (grams) of ammonium persulfate and 165parts-by-weight (grams) of deionized water was then charged into theflask over 15 minutes. The temperature rose from 50° C. to 80° C. due topolymerization exotherm. The mixture was held at 75° C. for anadditional hour. After cooling to 40° C., 1.2 parts-by-weight (grams) ofFOAMKILL® 649 (non-silicone defoamer, available from Crucible ChemicalCompany), 25 parts-by-weight (grams) of ACTICIDE® MBS (a microbiocidecomprising a mixture of 1,2-benzisothiazolin-3-one and2-methyl-4-isothiazolin-3-one, available from Thor GmbH), and 55parts-by-weight (grams) of deionized water were charged into the flaskand mixed for an additional 15 minutes. The resulting latex had a solidscontent of 38.6% and an average particle size of 60 nm. The averageparticle size was determined with a Zetasize 3000HS following theinstructions in the Zetasize 3000HS manual.

A layer of the basecoat composition (Table 4, above) was applied underambient conditions by drawdown over the electrocoat on the substratepanels using a drawdown bar with a 1 mil gap. The applied basecoatlayers were dehydrated for 5 minutes at 80° C. The resulting layers haddry film thicknesses of about 27 micrometers.

A second coating composition was applied over the dehydrated basecoatlayers to form second coating layers over each panel. The second coatingcomposition comprised a combination of a 1,1-di-activated vinyl compoundand a multifunctional form thereof (a mixture of diethyl methylenemalonate and a transesterification adduct of diethyl methylene malonateand 1,6-hexanediol, as described in U.S. Publication No. 2014/0329980).The second coating layers were applied under ambient conditions bydrawdown over the dehydrated basecoat layers using a drawdown bar with 2mil and 4 mil gaps (corresponding to dry film thicknesses of about 30-40micrometers and 50-60 micrometers, respectively).

The cure response of the second coating layers was monitored underambient conditions by measuring the time from application until thelayers were dry-to-touch (determined by manually touching the secondcoating layers with a gloved finger). Both the 30-40 μm DFT and the50-60 μm DFT layers achieved a dry-to-touch state under ambientconditions between 30-45 minutes after application. Additionally,beginning at 60 minutes after the application of the second coatinglayers, the coating hardness was measured using a standard HM2000Fischer MicroHardness tester. The results are reported in Table 9(hardnesses reported in units of N/mm²).

TABLE 9 Time (from application) 30-40 μm DFT layer 50-60 μm DFT layer 10minutes wet wet 20 minutes wet wet 30 minutes less wet less wet 45minutes dry dry 60 minutes dry dry 19 N/mm² 37 N/mm² 180 minutes 25N/mm² 52 N/mm² 3 days 66 N/mm² 107 N/mm² 4 days 75 N/mm² 111 N/mm² 5days 76 N/mm² 112 N/mm²

A methyl ethyl ketone solvent double rub test was also performed, asdescribed above in Example 1A, 60 minutes after application of thesecond coating layers. The second coating layer survived the 100 methylethyl ketone double rubs with no visible damage. An acetone solventdouble rub test was also performed 5 days after application of thesecond coating layer (the acetone double rub test was analogous to themethyl ethyl ketone double rub test, only acetone was used instead ofmethyl ethyl ketone). The second coating layer survived the 100 acetonedouble rubs with no visible damage.

Example 5B: Comparative Multi-Layer Coating System

Example 5A was repeated but the coating composition comprising a mixtureof diethyl methylene malonate and a transesterification adduct ofdiethyl methylene malonate and 1,6-hexanediol was applied directly over4-inch by 12-inch cold-rolled steel substrate panels pre-coated withED-6670 electrocoat (electrocoat available from PPG Industries, Inc.,and substrate panels available in pre-coated form from ACT Test PanelsLLC). No intermediate basecoat was applied between the electrocoat layerand the coating layer comprising the mixture of diethyl methylenemalonate and a transesterification adduct of diethyl methylene malonateand 1,6-hexanediol. The applied coating layer remained in a liquid stateafter five days from application.

Without intending to be bound by any theory, it is believed thatresidual amine (e.g., dimethylethanolamine) in the dehydrated basecoatlayers in Example 5A functioned as an activator compound that activatedanionic polymerization of the diethyl methylene malonate and thetransesterification adduct of diethyl methylene malonate and1,6-hexanediol in the second coating layer. In Example 5B, however, thecured electrocoat layer did not contain sufficient amounts of and/orsufficiently mobile amine compounds to activate anionic polymerizationin the overlying coating layer.

Example 6: Curable Compositions Comprising a 1,1-Di-Activated VinylCompound and an Ionic Liquid Activator, Optionally a Polythiol, andOptionally an Extender

A composition was provided comprising a 1,1-di-activated vinyl compoundand a multifunctional form thereof (a combination of diethyl methylenemalonate and a transesterification adduct of diethyl methylene malonateand 1,6-hexanediol). An ionic liquid was provided comprising analkylimidazolinium phthalate. A tetrafunctional polythiol was providedcomprising pentaerythritol tetra(3-mercaptoproprionate). An extender wasprovided comprising a vinyl polymer prepared using an ethylenicallyunsaturated carboxylic acid anhydride. The crosslinker composition (orunreacted diethyl methylene malonate), the ionic liquid, the polythiol,and the extender were combined together in the amounts provided in Table10 to form curable compositions.

TABLE 10 Crosslinker Ionic Composition¹ DEMM² Liquid³ Polythiol⁴Extender⁵ Sample (g) (g) (g) (g) (g) A — 2.0 0.03 — B 2.0 — 0.04 — C —2.0 0.07 — 1.00 D 2.0 — 0.09 — 0.50 E 2.0 — — 1.39 F 2.0 — 0.02 1.39 G2.0 — 0.07 1.39 1.00 ¹A mixture of diethyl methylene malonate and atransesterification adduct of diethyl methylene malonate and1,6-hexanediol, as described in U.S. Publication No. 2014/0329980.²Unreacted diethyl methylene malonate (monomeric). ³Analkylimidazolinium phthalate, available as IL-002 from Sanyo ChemicalIndustries, Ltd. ⁴Pentaerythritol tetra(3-mercaptoproprionate),available as THIOCURE ® PETMP, available from Bruno Bock ChemischeFabrik GmbH & Co KG. ⁵Example 1 in U.S. Pat. No. 4,798,745, column 10,line 40-column 11, line, 22, incorporated by reference into thisspecification.

The components of the curable compositions listed in Table 10 were mixedtogether in vials at room temperature. The curable compositions wereevaluated for gel time, and select formulations were evaluated forcoating film drying and curing properties (tack-free time) and solventresistance (MEK double rub test). Gel time was measured as the timeelapsed after combining all ingredients until the composition did notdemonstrate a visually observable flow when the vial containing thecomposition was inverted.

Coating films were prepared by applying the curable compositions listedin Table 10 over 10.16 cm by 30.18 cm cold-rolled steel substrate panelspre-coated with ED-6060 electrocoat (electrocoat available from PPGIndustries, Inc., and substrate panels available in pre-coated form fromACT Test Panels LLC). The coatings were applied immediately upon mixingby drawdown over the electrocoat on the substrate panels using adrawdown bar with a 2-4 mil gap (50-102 micrometers). Tack-free time wasmeasured as the amount of time required for a coating to achieve a levelof dryness such that upon the application and removal of a cotton ballno cotton fibers were transferred to the coating surface. MEK doublerubs (MEK DR) are reported as the number of double rubs performed byhand with a methyl ethyl ketone soaked rag required to dissolve thecoating such that the substrate is visible, up to a maximum number of100 MEK DR. The gel time, tack-free time, and MEK DR results arereported in Table 11.

TABLE 11 Tack-Free Time Tack-Free Time Gel (ambient (after 60° C. bakeMEK Sample Time temperature) for 10 minutes) DR A 3 min. 3 min. — — B 6min. 7 min. — — C >1 hour >1 hour 0 min.  0 D 30 min. — 0 min. 100 E 3hour >3 hour — — F <1 min. — — — G 10 min. >1 hour — —

The gel time and tack-free time of Samples A and B show that the ionicliquid was effective at polymerizing the DEMM and the crosslinkercomposition both in the vial and as a coating film applied onto a panel.It is noted that the short gel time and tack-free time of Samples A andB indicate rapid polymerization of the DEMM or DEMM crosslinker. SampleC was similar to Sample A but it further comprised the extender, whichprovided for a longer gel time and tack-free time at ambient conditions.Upon a brief bake (60° C. for 10 minutes), Sample C formed a tack-freecoating, but did not survive any MEK DR, which was unsurprising becausethe reaction product is believed to be an un-crosslinked linear polymerformed from anionic polymerization of the DEMM monomer. Sample D wassimilar to Sample B but it further comprised the extender, whichprovided for a longer gel time and tack-free time at ambient conditions.Upon a brief bake (60° C. for 10 minutes), Sample D formed a tack-freecoating that survived 100 MEK DR, indicating it formed asolvent-resistant crosslinked coating.

Sample E, which contained no ionic liquid, exhibited a relatively slowreaction of the crosslinker composition and the polythiol as indicatedby the long gel time and tack-free time. Sample F, which was is similarto Sample E but contained added ionic liquid, exhibited a substantiallyfaster reaction as indicated by the gel time under one minute. In fact,the reaction of Sample F upon initial mixing was so fast that it was notpossible to apply the composition as a coating film on a substrate panelbefore the composition was too viscous to apply. Sample G was similar toSample F but further comprised added extender. The addition of theextender resulted in an intermediate gel time of 10 minutes, as comparedto over 3 hours for Sample E and less than one minute for Sample F,which provides a more practical pot life for the composition.

These examples demonstrate the utility of ionic liquid for activatingthe cure of 1,1-di-activated vinyl compounds and multifunctional formsthereof, alone or in combination with polyfunctional materials such aspolyols, polyamines, polythiols, and/or polycarbamates. The use of anextender to control the reaction rate was also demonstrated, therebyproviding control over pot life and cure response, and facilitatinglonger gel times that extend the usable application time of thecompositions while still maintaining reasonably fast curing kinetics.

ASPECTS OF THE INVENTION

Aspects of the invention include, but are not limited to, the followingnumbered clauses.

1. A multi-layer curable composition comprising: a first curablecomposition layer applied over at least a portion of a substrate; and asecond curable composition layer applied over at least a portion of thefirst curable composition layer; wherein the first curable compositionlayer and the second curable composition layer both independentlycomprise a polymeric resin; and wherein the first curable compositionlayer and/or the second curable composition layer, when cured, comprisea polymerization reaction product of a 1,1-di-activated vinyl compound,or a multifunctional form thereof, or a combination thereof.

2. The multi-layer curable composition of clause 1, wherein the1,1-di-activated vinyl compound comprises a methylene dicarbonylcompound, a dihalo vinyl compound, a dihaloalkyl disubstituted vinylcompound, or a cyanoacrylate compound, or a multifunctional form of anythereof, or a combination of any thereof.

3. The multi-layer curable composition of clause 1 or clause 2, whereinthe first curable composition layer and/or the second curablecomposition layer, when cured, comprise a polymerization reactionproduct of a dialkyl methylene malonate, a diaryl methylene malonate, amultifunctional form of a dialkyl methylene malonate, or amultifunctional form of a diaryl methylene malonate, or a combination ofany thereof.

4. The multi-layer curable composition of clause 3, wherein the firstcurable composition layer and/or the second curable composition layer,when cured, comprise a polymerization reaction product of diethylmethylene malonate and a multifunctional form of diethyl methylenemalonate, wherein the multifunctional form of diethyl methylene malonatecomprises a transesterification adduct of diethyl methylene malonate andat least one polyol.

5. The multi-layer curable composition of clause 4, wherein thetransesterification adduct of diethyl methylene malonate and at leastone polyol comprises a transesterification adduct of diethyl methylenemalonate and a diol.

6. The multi-layer curable composition of clause 5, wherein the diolcomprises 1,5-pentane diol and/or 1,6-hexanediol.

7. The multi-layer curable composition of any one of clauses 1-6,wherein: (i) the first curable composition layer comprises an activatorcompound that activated polymerization reactions in the second coatinglayer when the second coating layer was applied over the first coatinglayer; or (ii) the second curable composition layer comprises anactivator compound that activates polymerization reactions in the firstcoating layer upon application of the second curable composition overthe first curable composition layer.

8. The multi-layer curable composition of clause 7, wherein theactivator compound comprises a tertiary amine compound.

9. The multi-layer curable composition of clause 8, wherein theactivator compound comprises 2-(dimethylamino)ethanol and/or1,4-diazabicyclo[2.2.2]octane.

10. The multi-layer curable composition of clause 7, wherein theactivator compound comprises an ionic liquid.

11. The multi-layer curable composition of any one of clauses 1-10,wherein the first curable composition layer comprises a curablecomposition that cures when heated at a temperature of less than 500°C., and wherein the second curable composition layer comprises thepolymerization reaction product.

12. The multi-layer curable composition of any one of clauses 1-11,wherein the first coating layer does not comprise melamine resin orformaldehyde condensates.

13. The multi-layer coating of any one of clauses 1-11, wherein thefirst curable composition layer comprises a thermoset resin comprisingacrylic resin, polyester resin, polyurethane resin, polyurea resin,polyether resin, polythioether resin, polycarbonate resin, polycarbamateresin, epoxy resin, phenolic resin, or aminoplast resin, or acombination of any thereof, and wherein the second curable compositionlayer comprises a clearcoat layer comprising the polymerization reactionproduct.

14. The multi-layer coating of any one of clauses 1-12, wherein thefirst curable composition layer comprises the polymerization reactionproduct, and wherein the first curable composition layer is applieddirectly onto a metallic substrate.

15. The multi-layer curable composition of clauses 1-12, wherein thefirst curable composition layer comprises the polymerization reactionproduct, and wherein the first curable composition layer is applieddirectly onto a non-metallic substrate.

16. The substrate of clauses 1-15, wherein the substrate is polymeric.

17. The substrate of clauses 1-16, where in the non-metallic substrateis an automobile component.

18. The multi-layer coating of any one of clauses 1-13, wherein thesubstrate comprises an electrodeposited curable composition layer andthe first curable composition layer is applied over the electrodepositedcoating layer.

19. The multi-layer curable composition of any one of clauses 1-18,wherein the curable composition layer comprising the polymerizationreaction product of the 1,1-di-activated vinyl compound, ormultifunctional form thereof, or combination thereof, further comprisesan extender.

20. The multi-layer curable composition of clause 19, wherein theextender comprises an anhydride-containing vinyl polymer.

21. The multi-layer curable composition of clause 20, wherein theanhydride-containing vinyl polymer comprises maleic anhydride monomerresidues.

22. An article comprising the multi-layer curable composition of any oneof clauses 1-21 deposited over a surface of the article.

23. The article of clause 22, wherein the article comprises a vehiclecomponent or a free-standing structure.

24. A process for curable composition a substrate comprising: applying afirst curable composition layer over at least a portion of a substrate;applying a second curable composition layer over at least a portion ofthe first curable composition layer; and curing the first curablecomposition layer and/or the second curable composition layer; whereinthe first curable composition layer and the second curable compositionlayer both independently comprise a polymeric resin; and wherein thefirst curable composition layer and/or the second curable compositionlayer, when cured, comprise a polymerization reaction product of a1,1-di-activated vinyl compound, or a multifunctional form thereof, or acombination thereof.

25. The process of clause 24, wherein the 1,1-di-activated vinylcompound comprises a methylene dicarbonyl compound, a dihalo vinylcompound, a dihaloalkyl disubstituted vinyl compound, or a cyanoacrylatecompound, or a multifunctional form of any thereof, or a combination ofany thereof.

26. The process of clause 24 or clause 25, wherein the curing of thefirst curable composition layer and/or the second curable compositionlayer comprises spraying an activator solution over and/or under atleast a portion of the first curable composition layer and/or the secondcurable composition layer.

27. The process of clause 26, wherein the activator solution comprises atertiary amine compound.

28. The process of clause 27, wherein the activator solution comprises1,4-diazabicyclo[2.2.2]octane and/or 2-(dimethylamino)ethanol.

29. The process of any one of clauses 24-28, wherein: (i) the firstcurable composition layer comprises an activator compound, and whereinthe curing of the second curable composition layer comprises activatinga polymerization reaction in the second curable composition layer withthe activator compound in the first curable composition layer; or (ii)the second curable composition layer comprises an activator compound,and wherein the curing of the first curable composition layer comprisesactivating a polymerization reaction in the first curable compositionlayer with the activator compound in the second curable compositionlayer.

30. The process of clause 29, wherein the activator compound comprises atertiary amine compound.

31. The process of clause 30, wherein the activator compound comprises2-(dimethylamino)ethanol and/or 1,4-diazabicyclo[2.2.2]octane.

32. The process of clause 29, wherein the activator compound comprisesan ionic liquid.

33. The process of any one of clauses 24-32, wherein at least one of thefirst curable composition layer and/or the second curable compositionlayer, when cured, comprises a polymerization reaction product of adialkyl methylene malonate, a diaryl methylene malonate, amultifunctional form of a dialkyl methylene malonate, or amultifunctional form of a diaryl methylene malonate, or a combinationthereof.

34. The process of clause 33, wherein the first curable compositionlayer and/or the second curable composition layer comprises apolymerization reaction product of diethyl methylene malonate and amultifunctional form of diethyl methylene malonate, wherein themultifunctional form of diethyl methylene malonate comprises atransesterification adduct of diethyl methylene malonate and at leastone polyol.

35. The process of clause 34, wherein the transesterification adduct ofdiethyl methylene malonate and at least one polyol comprises atransesterification adduct of diethyl methylene malonate and a diol.

36. The process of any one of clauses 24-35, wherein the first curablecomposition layer comprises a curable composition that cures when heatedat a temperature of less than 500° C., and wherein the second curablecomposition layer comprises the polymerization reaction product

37. The process of any one of clauses 24-36, wherein the first curablecomposition layer does not comprise melamine resin or formaldehydecondensates.

38. The process of any one of clauses 24-37, wherein the first curablecomposition layer, when cured, comprises a thermosetting resincomprising acrylic resin, polyester resin, polyurethane resin, polyurearesin, polyether resin, polythioether resin, polycarbonate resin,polycarbamate resin, epoxy resin, phenolic resin, or aminoplast resin,or a combination of any thereof, and wherein the second curablecomposition layer, when cured, comprises a clearcoat layer comprisingthe reaction product.

39. The process of any one of clauses 24-37, wherein the first curablecomposition layer, when cured, comprises the polymerization reactionproduct, and wherein the first curable composition layer is applieddirectly onto a metallic substrate.

40. The process of any one of clauses 24-38, wherein the substratecomprises an electrodeposited curable composition layer and the firstcoating layer is applied over the electrodeposited curable compositionlayer.

41. The process of any one of clauses 24-40, wherein the curablecomposition layer comprising the polymerization reaction product of the1,1-di-activated vinyl compound, or multifunctional form thereof, orcombination thereof, further comprises an extender.

42. The process of clause 41, wherein the extender comprises ananhydride-containing vinyl polymer.

43. The process of clause 42, wherein the anhydride-containing vinylpolymer comprises maleic anhydride monomer residues.

Various features and characteristics are described in this specificationto provide an understanding of the composition, structure, production,function, and/or operation of the invention, which includes thedisclosed compositions, coatings, and processes. It is understood thatthe various features and characteristics of the invention described inthis specification can be combined in any suitable manner, regardless ofwhether such features and characteristics are expressly described incombination in this specification. The Inventors and the Applicantexpressly intend such combinations of features and characteristics to beincluded within the scope of the invention described in thisspecification. As such, the claims can be amended to recite, in anycombination, any features and characteristics expressly or inherentlydescribed in, or otherwise expressly or inherently supported by, thisspecification. Furthermore, the Applicant reserves the right to amendthe claims to affirmatively disclaim features and characteristics thatmay be present in the prior art, even if those features andcharacteristics are not expressly described in this specification.Therefore, any such amendments will not add new matter to thespecification or claims, and will comply with written description,sufficiency of description, and added matter requirements, including therequirements under 35 U.S.C. § 112(a) and Article 123(2) EPC.

Any numerical range recited in this specification describes allsub-ranges of the same numerical precision (i.e., having the same numberof specified digits) subsumed within the recited range. For example, arecited range of “1.0 to 10.0” describes all sub-ranges between (andincluding) the recited minimum value of 1.0 and the recited maximumvalue of 10.0, such as, for example, “2.4 to 7.6,” even if the range of“2.4 to 7.6” is not expressly recited in the text of the specification.Accordingly, the Applicant reserves the right to amend thisspecification, including the claims, to expressly recite any sub-rangeof the same numerical precision subsumed within the ranges expresslyrecited in this specification. All such ranges are inherently describedin this specification such that amending to expressly recite any suchsub-ranges will comply with written description, sufficiency ofdescription, and added matter requirements, including the requirementsunder 35 U.S.C. § 112(a) and Article 123(2) EPC. Also, unless expresslyspecified or otherwise required by context, all numerical parametersdescribed in this specification (such as those expressing values,ranges, amounts, percentages, and the like) may be read as if prefacedby the word “about,” even if the word “about” does not expressly appearbefore a number. Additionally, numerical parameters described in thisspecification should be construed in light of the number of reportedsignificant digits, numerical precision, and by applying ordinaryrounding techniques. It is also understood that numerical parametersdescribed in this specification will necessarily possess the inherentvariability characteristic of the underlying measurement techniques usedto determine the numerical value of the parameter.

The invention(s) described in this specification can comprise, consistof, or consist essentially of the various features and characteristicsdescribed in this specification. The terms “comprise” (and any form ofcomprise, such as “comprises” and “comprising”), “have” (and any form ofhave, such as “has” and “having”), “include” (and any form of include,such as “includes” and “including”), and “contain” (and any form ofcontain, such as “contains” and “containing”) are open-ended linkingverbs. Thus, a composition, coating, or process that “comprises,” “has,”“includes,” or “contains” one or more features and/or characteristicspossesses those one or more features and/or characteristics, but is notlimited to possessing only those one or more features and/orcharacteristics. Likewise, an element of a composition, coating, orprocess that “comprises,” “has,” “includes,” or “contains” one or morefeatures and/or characteristics possesses those one or more featuresand/or characteristics, but is not limited to possessing only those oneor more features and/or characteristics, and may possess additionalfeatures and/or characteristics.

The grammatical articles “a,” “an,” and “the,” as used in thisspecification, including the claims, are intended to include “at leastone” or “one or more”, unless otherwise indicated. Thus, the articlesare used in this specification to refer to one or more than one (i.e.,to “at least one”) of the grammatical objects of the article. By way ofexample, “a component” means one or more components, and thus, possibly,more than one component is contemplated and can be employed or used inan implementation of the described compositions, coatings, andprocesses. Nevertheless, it is understood that use of the terms “atleast one” or “one or more” in some instances, but not others, will notresult in any interpretation where failure to use the terms limitsobjects of the grammatical articles “a,” “an,” and “the” to just one.Further, the use of a singular noun includes the plural, and the use ofa plural noun includes the singular, unless the context of the usagerequires otherwise.

Any patent, publication, or other document identified in thisspecification is incorporated by reference into this specification inits entirety unless otherwise indicated, but only to the extent that theincorporated material does not conflict with existing descriptions,definitions, statements, illustrations, or other disclosure materialexpressly set forth in this specification. As such, and to the extentnecessary, the express disclosure as set forth in this specificationsupersedes any conflicting material incorporated by reference. Anymaterial, or portion thereof, that is incorporated by reference intothis specification, but which conflicts with existing definitions,statements, or other disclosure material set forth herein, is onlyincorporated to the extent that no conflict arises between thatincorporated material and the existing disclosure material. Applicantreserves the right to amend this specification to expressly recite anysubject matter, or portion thereof, incorporated by reference. Theamendment of this specification to add such incorporated subject matterwill comply with written description, sufficiency of description, andadded matter requirements, including the requirements under 35 U.S.C. §112(a) and Article 123(2) EPC.

1-43. (canceled)
 44. A multi-layer curable composition comprising: afirst curable composition layer applied over at least a portion of asubstrate; and a second curable composition layer applied over at leasta portion of the first curable composition layer; wherein the firstcurable composition layer and the second curable composition layer bothindependently comprise a polymeric resin; and wherein the first curablecomposition layer and/or the second curable composition layer, whencured, comprise a polymerization reaction of a methylene dicarbonylcompound, a multifunctional form thereof, or a combination of anythereof.
 45. The multi-layer curable composition of claim 44, whereinthe methylene dicarbonyl compound comprises a dialkyl methylenemalonate, a diaryl methylene malonate, a diethyl methylene malonate, ora combination thereof.
 46. The multi-layer curable composition of claim44, wherein the first curable composition layer and/or the secondcurable composition layer, when cured, comprise a polymerizationreaction product of diethyl methylene malonate and a multifunctionalform of diethyl methylene malonate, wherein the multifunctional form ofdiethyl methylene malonate comprises a transesterification adduct ofdiethyl methylene malonate and at least one polyol.
 47. The multi-layercurable composition of claim 44, wherein: (i) the first curablecomposition layer comprises an activator compound that activatedpolymerization reactions in the second curable composition layer whenthe second curable composition layer was applied over the first curablecomposition layer; or (ii) the second curable composition layercomprises an activator compound that activates polymerization reactionsin the first curable composition layer upon application of the secondcurable composition layer over the first curable composition layer. 48.The multi-layer curable composition of claim 44, wherein the firstcurable composition layer comprises a thermoset resin comprising acrylicresin, polyester resin, polyurethane resin, polyurea resin, polyetherresin, polythioether resin, polycarbonate resin, polycarbamate resin,epoxy resin, phenolic resin, or aminoplast resin, or a combination ofany thereof, and wherein the second curable composition layer comprisesa clearcoat layer comprising the polymerization reaction product. 49.The multi-layer curable composition of claim 44, wherein the firstcurable composition layer comprises the polymerization reaction product,and wherein the first curable composition layer is applied directly ontoa metallic substrate.
 50. The multi-layer curable composition of claim44, wherein the first curable composition layer comprises thepolymerization reaction product, and wherein the first curablecomposition layer is applied directly onto a non-metallic substrate. 51.The multi-layer curable composition of claim 44, wherein the substratecomprises an electrodeposited curable composition layer and the firstcurable composition layer is applied over the electrodeposited curablecomposition layer.
 52. The multi-layer curable composition of claim 44,wherein the curable composition layer comprising the polymerizationreaction product further comprises an extender.
 53. An articlecomprising the multi-layer curable composition of claim 44 depositedover a surface of the article.
 54. The article of claim 53, wherein thearticle comprises a vehicle component or a free-standing structure. 55.A process for applying a curable composition to a substrate comprising:applying a first curable composition layer over at least a portion of asubstrate; applying a second curable composition layer over at least aportion of the first curable composition layer; and curing the firstcurable composition layer and/or the second curable composition layer;wherein the first curable composition layer and the second coating layerboth independently comprise a polymeric resin; and wherein the firstcurable composition layer and/or the second curable composition layer,when cured, comprise a polymerization reaction product of a methylenedicarbonyl compound, or a multifunctional form of a diaryl methylenemalonate, or a combination of any thereof.
 56. The process of claim 55,wherein the curing of the first curable composition layer and/or thesecond curable composition layer comprises applying an activatorsolution over and/or under at least a portion of the first curablecomposition layer and/or the second curable composition layer.
 57. Theprocess of claim 55, wherein: the first curable composition layercomprises an activator compound, and wherein the curing of the secondcurable composition layer comprises activating a polymerization reactionin the second curable composition layer with the activator compound inthe first curable composition layer; or the second curable compositionlayer comprises an activator compound, and wherein the curing of thefirst curable composition layer comprises activating a polymerizationreaction in the first curable composition layer with the activatorcompound in the second coating layer.
 58. The process of claim 55,wherein the methylene dicarbonyl compound comprises a dialkyl methylenemalonate, a diaryl methylene malonate, a diethyl methylene malonate, ora combination thereof.
 59. The process of claim 55, wherein the firstcurable composition layer and/or the second curable composition layer,when cured, comprise a polymerization reaction product of diethylmethylene malonate and a multifunctional form of diethyl methylenemalonate, wherein the multifunctional form of diethyl methylene malonatecomprises a transesterification adduct of diethyl methylene malonate andat least one polyol.
 60. The process of claim 55, wherein the firstcurable composition layer, when cured, comprises a thermoset resincomprising acrylic resin, polyester resin, polyurethane resin, polyurearesin, polyether resin, polythioether resin, polycarbonate resin,polycarbamate resin, epoxy resin, phenolic resin, or aminoplast resin,or a combination of any thereof, and wherein the second coating layer,when cured, comprises a clearcoat layer comprising the polymerizationreaction product.
 61. The process of claim 55, wherein the first curablecomposition layer, when cured, comprises the polymerization reactionproduct, and wherein the first curable composition layer is applieddirectly onto a metallic substrate or a non-metallic substrate.
 62. Theprocess of claim 55, wherein the substrate comprises an electrodepositedcurable composition layer and the first curable composition layer isapplied over the electrodeposited curable composition layer.
 63. Theprocess of claim 55, wherein the curable composition layer comprisingthe polymerization reaction product, further comprises an extender.